Processes for producing hydroxyaldehydes

ABSTRACT

This invention relates in part to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, which comprise subjecting one or more substituted or unsubstituted alkadienes, e.g., butadiene, to reductive hydroformylation in the presence of a reductive hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and hydroformylation in the presence of a hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce one or more substituted or unsubstituted hydroxyaldehydes. The substituted and unsubstituted hydroxyaldehydes produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactone. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted hydroxyaldehydes as principal product(s) of reaction.

This application claims the benefit of provisional U.S. patentapplication Ser. Nos. 60/016259, 60/016378, 60/016174 and 60/016263, allfiled Apr. 24, 1996, and all of the disclosures of which areincorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION Technical Field

This invention relates in part to processes for selectively producingone or more substituted or unsubstituted hydroxyaldehydes, e.g.,6-hydroxyhexanals. This invention also relates in part to reactionmixtures containing one or more substituted or unsubstitutedhydroxyaldehydes, e.g., 6-hydroxyhexanals, as the principal product(s)of reaction.

BACKGROUND OF THE INVENTION

Hydroxyaldehydes, e.g., 6-hydroxyhexanals, are valuable intermediateswhich are useful, for example, in the production of epsiloncaprolactone, epsilon caprolactam, adipic acid and 1,6-hexanediol. Theprocesses currently used to produce hydroxyaldehydes have variousdisadvantages. For example, the starting materials used to produce6-hydroxyhexanals are relatively expensive. In addition, the selectivityto 6-hydroxyhexanals in prior art processes has been low. Accordingly,it would be desirable to selectively produce hydroxyaldehydes from arelatively inexpensive starting material and by a process which can beemployed commercially.

DISCLOSURE OF THE INVENTION

It has been discovered that alkadienes or pentenals can be converted tolinear hydroxyaldehydes in high selectivities. It has also beendiscovered that unsaturated alcohols, e.g., alcohols possessing internalolefinic unsaturation, can be hydroformylated to hydroxyaldehydes, e.g.,terminal aldehydes, in high normal:branched isomer ratios, e.g.,3-penten-1-ols hydroformylated to 6-hydroxyhexanals in highnormal:branched isomer ratios. In particular it has been surprisinglydiscovered that butadiene can be converted to linear 6-hydroxyhexanals,e.g., 6-hydroxyhexanal, by employing catalysts having reductivehydroformylation/hydroformylation/isomerization capabilities.

This invention relates to processes for producing one or moresubstituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals,which comprise subjecting one or more substituted or unsubstitutedalkadienes, e.g., butadiene, to reductive hydroformylation in thepresence of a reductive hydroformylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and hydroformylation inthe presence of a hydroformylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce one or moresubstituted or unsubstituted hydroxyaldehydes.

This invention also relates to processes for producing one or moresubstituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals,which comprise subjecting one or more substituted or unsubstitutedpentenals to reductive hydroformylation in the presence of a reductivehydroformylation catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, to produce one or more substituted or unsubstitutedhydroxyaldehydes.

This invention further relates to processes for producing one or moresubstituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals,which comprise subjecting one or more substituted or unsubstitutedunsaturated alcohols, preferably having at least 4 carbon atoms, e.g.,penten-1-ols, to hydroformylation in the presence of a hydroformylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce said one or more substituted or unsubstituted hydroxyaldehydes.

This invention yet further relates to processes for producing one ormore substituted or unsubstituted hydroxyaldehydes, e.g.,6-hydroxyhexanals, which comprise: (a) subjecting one or moresubstituted or unsubstituted alkadienes, e.g., butadiene, to reductivehydroformylation in the presence of a reductive hydroformylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce one or more substituted or unsubstituted unsaturated alcohols;and (b) subjecting said one or more substituted or unsubstitutedunsaturated alcohols to hydroformylation in the presence of ahydroformylation catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, to produce said one or more substituted or unsubstitutedhydroxyaldehydes. The reductive hydroformylation reaction conditions instep (a) and the hydroformylation reaction conditions in step (b) may bethe same or different, and the reductive hydroformylation catalyst instep (a) and the hydroformylation catalyst in step (b) may be the sameor different.

This invention also relates to processes for producing one or moresubstituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals,which comprises reacting one or more substituted or unsubstitutedalkadienes, e.g., butadienes, with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce one or more substituted or unsubstituted unsaturatedalcohols, e.g., penten-1-ols, and reacting said one or more substitutedor unsubstituted unsaturated alcohols with carbon monoxide and hydrogenin the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said one or more substituted or unsubstitutedhydroxyaldehydes. In a preferred embodiment, the metal-ligand complexcatalysts are metal-organophosphorus ligand complex catalysts.

This invention further relates to processes for producing one or moresubstituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals,which comprises reacting one or more substituted or unsubstitutedpentenals with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, and optionally free ligand to produce one or moresubstituted or unsubstituted hydroxyaldehydes. In a preferredembodiment, the metal-ligand complex catalyst is ametal-organophosphorus ligand complex catalyst.

This invention yet further relates to processes for producing one ormore substituted or unsubstituted hydroxyaldehydes, e.g.,6-hydroxyhexanals, which comprise reacting one or more substituted orunsubstituted unsaturated alcohols, preferably having at least 4 carbonatoms, e.g., penten-1-ols, with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said one or more substituted or unsubstitutedhydroxyaldehydes.

This invention also relates to processes for producing one or moresubstituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals,which comprises: (a) reacting one or more substituted or unsubstitutedalkadienes, e.g., butadienes, with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce one or more substituted or unsubstituted unsaturatedalcohols, e.g., penten-1-ols, and (b) reacting said one or moresubstituted or unsubstituted unsaturated alcohols with carbon monoxideand hydrogen in the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said one or more substituted or unsubstitutedhydroxyaldehydes. The reductive hydroformylation reaction conditions instep (a) and the hydroformylation reaction conditions in step (b) may bethe same or different, and the reductive hydroformylation catalyst instep (a) and the hydroformylation catalyst in step (b) may be the sameor different.

This invention further relates in part to a process for producing abatchwise or continuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g.,6-hydroxyhexanal;

(2) optionally one or more substituted or unsubstituted penten-1-ols,e.g., cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

(5) optionally one or more substituted or unsubstituted pentan-1-ols;

(6) optionally one or more substituted or unsubstituted valeraldehydes;

(7) optionally one or more substituted or unsubstituted pentenals, e.g.,cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenaland/or 4-pentenal;

(8) optionally one or more substituted or unsubstituted 1,6-hexanedials,e.g., adipaldehyde;

(9) optionally one or more substituted 1,5-pentanedials, e.g.,2-methylglutaraldehyde;

(10) optionally one or more substituted 1,4-butanedials, e.g.,2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and

(11) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

wherein the weight ratio of component (1) to the sum of components (2),(3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1,preferably greater than about 0.25, more preferably greater than about1.0; and the weight ratio of component (11) to the sum of components(1), (2), (3), (4), (5), (6), (7), (8), (9) and (10) is about 0 to about100, preferably about 0.001 to about 50;

which process comprises reacting one or more substituted orunsubstituted butadienes, e.g., butadiene, with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce one or more substituted or unsubstituted penten-1-olsand reacting said one or more substituted or unsubstituted penten-1-olswith carbon monoxide and hydrogen in the presence of a metal-ligandcomplex catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, and optionally free ligand to produce said batchwise orcontinuously generated reaction mixture. In a preferred embodiment, themetal-ligand complex catalysts are metal-organophosphorus ligand complexcatalysts.

This invention yet further relates in part to a process for producing abatchwise or continuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g.,6-hydroxyhexanal;

(2) optionally one or more substituted or unsubstituted penten-1-ols,e.g., cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

(5) optionally one or more substituted or unsubstituted pentan-1-ols;

(6) optionally one or more substituted or unsubstituted valeraldehydes;and

(7) one or more substituted or unsubstituted pentenals, e.g.,cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenaland/or 4-pentenal;

wherein the weight ratio of component (1) to the sum of components (2),(3), (4), (5) and (6) is greater than about 0.1, preferably greater thanabout 0.25, more preferably greater than about 1.0; and the weight ratioof component (7) to the sum of components (1), (2), (3), (4), (5) and(6) is about 0 to about 100, preferably about 0.001 to about 50;

which process comprises reacting one or more substituted orunsubstituted pentenals with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said batchwise or continuously generated reactionmixture. In a preferred embodiment, the metal-ligand complex catalyst isa metal-organophosphorus ligand complex catalyst.

This invention also relates in part to a process for producing abatchwise or continuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g.,6-hydroxyhexanal;

(2) one or more substituted or unsubstituted penten-1-ols, e.g.,cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal; and

(5) optionally one or more substituted or unsubstituted valeraldehydes;

wherein the weight ratio of component (1) to the sum of components (3),(4) and (5) is greater than about 0.1, preferably greater than about0.25, more preferably greater than about 1.0; and the weight ratio ofcomponent (2) to the sum of components (1), (3), (4) and (5) is about 0to about 100, preferably about 0.001 to about 50;

which process comprises reacting one or more substituted orunsubstituted penten-1-ols with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said batchwise or continuously generated reactionmixture.

This invention further relates in part to a process for producing abatchwise or continuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g.,6-hydroxyhexanal;

(2) optionally one or more substituted or unsubstituted penten-1-ols,e.g., cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

(5) optionally one or more substituted or unsubstituted pentan-1-ols;

(6) optionally one or more substituted or unsubstituted valeraldehydes;

(7) optionally one or more substituted or unsubstituted pentenals, e.g.,cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenaland/or 4-pentenal;

(8) optionally one or more substituted or unsubstituted 1,6-hexanedials,e.g., adipaldehyde;

(9) optionally one or more substituted 1,5-pentanedials, e.g.,2-methylglutaraldehyde;

(10) optionally one or more substituted 1,4-butanedials, e.g.,2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and

(11) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

wherein the weight ratio of component (1) to the sum of components (2),(3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1,preferably greater than about 0.25, more preferably greater than about1.0; and the weight ratio of component (11) to the sum of components(1), (2), (3), (4), (5), (6), (7), (8), (9) and (10) is about 0 to about100, preferably about 0.001 to about 50;

which process comprises: (a) reacting one or more substituted orunsubstituted butadienes, e.g., butadiene, with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce one or more substituted or unsubstituted penten-1-ols,and (b) reacting said one or more substituted or unsubstitutedpenten-1-ols with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, and optionally free ligand to produce said batchwiseor continuously generated reaction mixture. The reductivehydroformylation reaction conditions in step (a) and thehydroformylation reaction conditions in step (b) may be the same ordifferent, and the reductive hydroformylation catalyst in step (a) andthe hydroformylation catalyst in step (b) may be the same or different.

This invention yet further relates to a process for producing a reactionmixture comprising one or more substituted or unsubstitutedhydroxyaldehydes, e.g., 6-hydroxyhexanals, which process comprisesreacting one or more substituted or unsubstituted alkadienes, e.g.,butadienes, with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, and optionally free ligand to produce one or moresubstituted or unsubstituted unsaturated alcohols, e.g., penten-1-ols,and reacting said one or more substituted or unsubstituted unsaturatedalcohols with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, and optionally free ligand to produce said reactionmixture comprising one or more substituted or unsubstitutedhydroxyaldehydes. In a preferred embodiment, the metal-ligand complexcatalysts are metal-organophosphorus ligand complex catalysts.

This invention also relates to a process for producing a reactionmixture comprising one or more substituted or unsubstitutedhydroxyaldehydes, e.g., 6-hydroxyhexanals, which process comprisesreacting one or more substituted or unsubstituted pentenals with carbonmonoxide and hydrogen in the presence of a metal-ligand complexcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, andoptionally free ligand to produce said reaction mixture comprising oneor more substituted or unsubstituted hydroxyaldehydes. In a preferredembodiment, the metal-ligand complex catalyst is ametal-organophosphorus ligand complex catalyst.

This invention further relates to a process for producing a reactionmixture comprising one or more substituted or unsubstitutedhydroxyaldehydes, e.g., 6-hydroxyhexanals, which process comprisesreacting one or more substituted or unsubstituted unsaturated alcohols,preferably having at least 4 carbon atoms, e.g., penten-1-ols, withcarbon monoxide and hydrogen in the presence of a metal-ligand complexcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, andoptionally free ligand to produce said reaction mixture comprising oneor more substituted or unsubstituted hydroxyaldehydes.

This invention yet further relates to a process for producing a reactionmixture comprising one or more substituted or unsubstitutedhydroxyaldehydes, e.g., 6-hydroxyhexanals, which process comprises: (a)reacting one or more substituted or unsubstituted alkadienes, e.g.,butadienes, with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, and optionally free ligand to produce one or moresubstituted or unsubstituted unsaturated alcohols, e.g., penten-1-ols,and (b) reacting said one or more substituted or unsubstitutedunsaturated alcohols with carbon monoxide and hydrogen in the presenceof a metal-ligand complex catalyst, e.g., a metal-organophosphorusligand complex catalyst, and optionally free ligand to produce saidreaction mixture comprising one or more substituted or unsubstitutedhydroxyaldehydes. The reductive hydroformylation reaction conditions instep (a) and the hydroformylation reaction conditions in step (b) may bethe same or different, and the reductive hydroformylation catalyst instep (a) and the hydroformylation catalyst in step (b) may be the sameor different.

The processes of this invention can achieve high selectivities ofalkadienes, pentenals and penten-1-ols to 6-hydroxyhexanals, i.e.,selectivities of penten-1-ols to 6-hydroxyhexanals of at least 10% byweight and up to 85% by weight or greater may be achieved by theprocesses of this invention. Also, the processes of this invention canachieve high normal:branched isomer ratios, e.g., butadiene reductivehydroformylated/hydroformylated to 6-hydroxyhexanals in highnormal:branched isomer ratios.

This invention also relates in part to a batchwise or continuouslygenerated reaction mixture comprising:

(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g.,6-hydroxyhexanal;

(2) one or more substituted or unsubstituted penten-1-ols, e.g.,cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal; and

(5) optionally one or more substituted or unsubstituted valeraldehydes;

wherein the weight ratio of component (1) to the sum of components (3),(4) and (5) is greater than about 0.1, preferably greater than about0.25, more preferably greater than about 1.0; and the weight ratio ofcomponent (2) to the sum of components (1), (3), (4) and (5) is about 0to about 100, preferably about 0.001 to about 50.

This invention further relates in part to a batchwise or continuouslygenerated reaction mixture comprising:

(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g.,6-hydroxyhexanal;

(2) optionally one or more substituted or unsubstituted penten-1-ols,e.g., cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

(5) optionally one or more substituted or unsubstituted pentan-1-ols;

(6) optionally one or more substituted or unsubstituted valeraldehydes;and

(7) optionally one or more substituted or unsubstituted pentenals, e.g.,cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenaland/or 4-pentenal;

wherein the weight ratio of component (1) to the sum of components (2),(3), (4), (5) and (6) is greater than about 0.1, preferably greater thanabout 0.25, more preferably greater than about 1.0; and the weight ratioof component (7) to the sum of components (1), (2), (3), (4), (5) and(6) is about 0 to about 100, preferably about 0.001 to about 50.

This invention yet further relates in part to a batchwise orcontinuously generated reaction mixture comprising:

(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g.,6-hydroxyhexanal;

(2) optionally one or more substituted or unsubstituted penten-1-ols,e.g., cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

(3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

(4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

(5) optionally one or more substituted or unsubstituted pentan-1-ols;

(6) optionally one or more substituted or unsubstituted valeraldehydes;

(7) optionally one or more substituted or unsubstituted pentenals, e.g.,cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenaland/or 4-pentenal;

(8) optionally one or more substituted or unsubstituted 1,6-hexanedials,e.g., adipaldehyde;

(9) optionally one or more substituted 1,5-pentanedials, e.g.,2-methylglutaraldehyde;

(10) optionally one or more substituted 1,4-butanedials, e.g.,2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and

(11) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

wherein the weight ratio of component (1) to the sum of components (2),(3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1,preferably greater than about 0.25, more preferably greater than about1.0; and the weight ratio of component (11) to the sum of components(1), (2), (3), (4), (5), (6), (7), (8), (9) and (10) is about 0 to about100, preferably about 0.001 to about 50.

This invention also relates in part to a reaction mixture comprising oneor more substituted or unsubstituted hydroxyaldehydes, e.g.,6-hydroxyhexanals, in which said reaction mixture is prepared by aprocess which comprises reacting one or more substituted orunsubstituted alkadienes, e.g., butadienes, with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce one or more substituted or unsubstituted unsaturatedalcohols, e.g., penten-1-ols, and reacting said one or more substitutedor unsubstituted unsaturated alcohols with carbon monoxide and hydrogenin the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said reaction mixture comprising one or moresubstituted or unsubstituted hydroxyaldehydes. In a preferredembodiment, the metal-ligand complex catalysts aremetal-organophosphorus ligand complex catalysts.

This invention further relates in part to a reaction mixture comprisingone or more substituted or unsubstituted hydroxyaldehydes, e.g.,6-hydroxyhexanals, in which said reaction mixture is prepared by aprocess which comprises reacting one or more substituted orunsubstituted pentenals with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said reaction mixture comprising one or moresubstituted or unsubstituted hydroxyaldehydes. In a preferredembodiment, the metal-ligand complex catalyst is ametal-organophosphorus ligand complex catalyst.

This invention yet further relates in part to a reaction mixturecomprising one or more substituted or unsubstituted hydroxyaldehydes,e.g., 6-hydroxyhexanals, in which said reaction mixture is prepared by aprocess which comprises reacting one or more substituted orunsubstituted unsaturated alcohols, preferably having at least 4 carbonatoms, e.g., penten-1-ols, with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said reaction mixture comprising one or moresubstituted or unsubstituted hydroxyaldehydes.

This invention also relates in part to a reaction mixture comprising oneor more substituted or unsubstituted hydroxyaldehydes, e.g.,6-hydroxyhexanals, in which said reaction mixture is prepared by aprocess which comprises: (a) reacting one or more substituted orunsubstituted alkadienes, e.g., butadienes, with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce one or more substituted or unsubstituted unsaturatedalcohols, e.g., penten-1-ols, and (b) reacting said one or moresubstituted or unsubstituted unsaturated alcohols with carbon monoxideand hydrogen in the presence of a metal-ligand complex catalyst, e.g., ametal-organophosphorus ligand complex catalyst, and optionally freeligand to produce said reaction mixture comprising one or moresubstituted or unsubstituted hydroxyaldehydes. The reductivehydroformylation reaction conditions in step (a) and thehydroformylation reaction conditions in step (b) may be the same ordifferent, and the reductive hydroformylation catalyst in step (a) andthe hydroformylation catalyst in step (b) may be the same or different.

The reaction mixtures of this invention are distinctive insofar as theprocesses for their preparation achieve the generation of highselectivities of 6-hydroxyhexanals in a manner which can be suitablyemployed in a commercial process for the manufacture of6-hydroxyhexanals. In particular, the reaction mixtures of thisinvention are distinctive insofar as the processes for their preparationallow for the production of 6-hydroxyhexanals in relatively high yieldswithout generating large amounts of byproducts, e.g., pentanols andvaleraldehyde.

DETAILED DESCRIPTION

The reductive hydroformylation processes of this invention include, butare not limited to, converting one or more substituted or unsubstitutedconverting one or more substituted or unsubstituted pentenals to one ormore substituted or unsubstituted 1,6-hydroxyhexanals, and convertingone or more substituted or unsubstituted alkadienes to one or moresubstituted or unsubstituted penten-1-ols. As used herein, the term"reductive hydroformylation" is contemplated to include, but is notlimited to, all permissible hydroformylation, hydrogenation andisomerization processes which include converting one or more substitutedor unsubstituted pentenals to one or more substituted or unsubstituted1,6-hydroxyhexanals, and converting one or more substituted orunsubstituted alkadienes to one or more substituted or unsubstitutedpenten-1-ols. In general, the reductive hydroformylation step or stagecomprises reacting one or more substituted or unsubstituted pentenalswith carbon monoxide and hydrogen in the presence of a catalyst toproduce one or more substituted or unsubstituted 1,6-hydroxyhexanals,and reacting one or more substituted or unsubstituted alkadienes withcarbon monoxide and hydrogen in the presence of a catalyst to produceone or more substituted or unsubstituted penten-1-ols.

The reductive hydroformylation processes of this invention may beconducted in one or more steps or stages, preferably a one step process.The hydroformylation, hydrogenation and isomerization reactions may beconducted in any permissible sequence so as to produce one or moresubstituted or unsubstituted 1,6-hydroxyhexanals or penten-1-ols.

Illustrative hydroformylation steps or stages include, but are notlimited to, the following: (a) converting one or more substituted orunsubstituted alkadienes to one or more substituted or unsubstitutedpentenals; and (b) converting one or more substituted or unsubstitutedpenten-1-ols to one or more substituted or unsubstituted6-hydroxyhexanals.

Illustrative hydrogenation stages include, but are not limited to, thefollowing converting one or more substituted or unsubstituted pentenalsto one or more substituted or unsubstituted penten-1-ols.

Illustrative isomerization stages include, but are not limited to, thefollowing: (a) converting one or more substituted or unsubstituted2-pentenals and/or 3-pentenals to one or more substituted orunsubstituted 4-pentenals, and (b) converting one or more substituted orunsubstituted 2-penten-1-ols and/or 3-penten-1-ols to one or moresubstituted or unsubstituted 4-penten-1-ols.

Suitable reductive hydroformylation reaction conditions and processingtechniques and suitable reductive hydroformylation catalysts includethose described below for the hydroformylation and hydrogenation stepsor stages. The hydroformylation and hydrogenation steps or stagesemployed in the processes of this invention may be carried out asdescribed below.

While not wishing to be bound to any particular reaction mechanism, itis believed that the overall reductive hydroformylation reactiongenerally proceeds in one or more steps or stages. This invention is notintended to be limited in any manner by any particular reactionmechanism, but rather encompasses all permissible hydroformylation,hydrogenation and isomerization processes as described herein.

Hydroformylation Steps or Stages

The hydroformylation processes involve the production of aldehydes,e.g., 6-hydroxyhexanals or pentenals, by reacting an olefinic compound,e.g., penten-1-ols, or an alkadiene, with carbon monoxide and hydrogenin the presence of a metal-ligand complex catalyst and optionally freeligand in a liquid medium that also contains a solvent for the catalystand ligand. The processes may be carried out in a continuous single passmode in a continuous gas recycle manner or more preferably in acontinuous liquid catalyst recycle manner as described below. Thehydroformylation processing techniques employable herein may correspondto any known processing techniques such as preferably employed inconventional liquid catalyst recycle hydroformylation reactions. As usedherein, the term "hydroformylation" is contemplated to include, but isnot limited to, all permissible hydroformylation processes which involveconverting one or more substituted or unsubstituted olefinic compoundsor alkadienes to one or more substituted or unsubstituted aldehydes. Ingeneral, the hydroformylation step or stage comprises reacting one ormore substituted or unsubstituted penten-1-ols with carbon monoxide andhydrogen in the presence of a catalyst to produce one or moresubstituted or unsubstituted 6-hydroxyhexanals, and reacting one or moresubstituted or unsubstituted alkadienes with carbon monoxide andhydrogen in the presence of a catalyst to produce one or moresubstituted or unsubstituted pentenals.

The hydroformylation reaction mixtures employable herein includes anysolution derived from any corresponding hydroformylation process thatmay contain at least some amount of four different main ingredients orcomponents, i.e., the aldehyde product, a metal-ligand complex catalyst,optionally free ligand and an organic solubilizing agent for saidcatalyst and said free ligand, said ingredients corresponding to thoseemployed and/or produced by the hydroformylation process from whence thehydroformylation reaction mixture starting material may be derived. By"free ligand" is meant ligand that is not complexed with (tied to orbound to) the metal, e.g., rhodium atom, of the complex catalyst. It isto be understood that the hydroformylation reaction mixture compositionsemployable herein can and normally will contain minor amounts ofadditional ingredients such as those which have either been deliberatelyemployed in the hydroformylation process or formed in situ during saidprocess. Examples of such ingredients that can also be present includeunreacted olefin or alkadiene starting material, carbon monoxide andhydrogen gases, and in situ formed type products, such as saturatedhydrocarbons and/or unreacted isomerized or olefins corresponding to theolefin or alkadiene starting materials, and high boiling liquid aldehydecondensation byproducts, as well as other inert co-solvent typematerials or hydrocarbon additives, if employed.

The catalysts useful in the hydroformylation process includemetal-ligand complex catalysts. The permissible metals which make up themetal-ligand complexes include Group 8, 9 and 10 metals selected fromrhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe),nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixturesthereof, with the preferred metals being rhodium, cobalt, iridium andruthenium, more preferably rhodium, cobalt and ruthenium, especiallyrhodium. The permissible ligands include, for example, organophosphorus,organoarsenic and organoantimony ligands, or mixtures thereof,preferably organophosphorus ligands. The permissible organophosphorusligands which make up the metal-ligand complexes includeorganophosphines, e.g., mono-, di-, tri- and poly-(organophosphines),and organophosphites, e.g., mono-, di-, tri- andpoly-(organophosphites). Other permissible organophosphorus ligandsinclude, for example, organophosphonites, organophosphinites, aminophosphines and the like. Still other permissible ligands include, forexample, heteroatom-containing ligands such as described in U.S. patentapplication Ser. No. (D-17646-1), filed Mar. 10, 1997, the disclosure ofwhich is incorporated herein by reference. Mixtures of such ligands maybe employed if desired in the metal-ligand complex catalyst and/or freeligand and such mixtures may be the same or different. This invention isnot intended to be limited in any manner by the permissibleorganophosphorus ligands or mixtures thereof. It is to be noted that thesuccessful practice of this invention does not depend and is notpredicated on the exact structure of the metal-ligand complex species,which may be present in their mononuclear, dinuclear and/or highernuclearity forms. Indeed, the exact structure is not known. Although itis not intended herein to be bound to any theory or mechanisticdiscourse, it appears that the catalytic species may in its simplestform consist essentially of the metal in complex combination with theligand and carbon monoxide when used.

The term "complex" as used herein and in the claims means a coordinationcompound formed by the union of one or more electronically richmolecules or atoms capable of independent existence with one or moreelectronically poor molecules or atoms, each of which is also capable ofindependent existence. For example, the ligands employable herein, i.e.,organophosphorus ligands, may possess one or more phosphorus donoratoms, each having one available or unshared pair of electrons which areeach capable of forming a coordinate covalent bond independently orpossibly in concert (e.g., via chelation) with the metal. Carbonmonoxide (which is also properly classified as a ligand) can also bepresent and complexed with the metal. The ultimate composition of thecomplex catalyst may also contain an additional ligand, e.g., hydrogenor an anion satisfying the coordination sites or nuclear charge of themetal. Illustrative additional ligands include, e.g., halogen (Cl, Br,I), alkyl, aryl, substituted aryl, acyl, CF₃, C₂ F₅, CN, (R)₂ PO andRP(O)(OH)O (wherein each R is the same or different and is a substitutedor unsubstituted hydrocarbon radical, e.g., the alkyl or aryl), acetate,acetylacetonate, SO₄, BF₄, PF₆, NO₂, NO₃, CH₃, CH₂ ═CHCH₂, CH₃ CH═CHCH₂,C₆ H₅ CN, CH₃ CN, NO, NH₃, pyridine, (C₂ H₅)₃ N, mono-olefins, diolefinsand triolefins, tetrahydrofuran, and the like. It is of course to beunderstood that the complex species are preferably free of anyadditional organic ligand or anion that might poison the catalyst andhave an undue adverse effect on catalyst performance. It is preferred inthe metal-ligand complex catalyzed hydroformylation reactions that theactive catalysts be free of halogen and sulfur directly bonded to themetal, although such may not be absolutely necessary. Preferredmetal-ligand complex catalysts include rhodium-organophosphine ligandcomplex catalysts and rhodium-organophosphite ligand complex catalysts.

The number of available coordination sites on such metals is well knownin the art. Thus the catalytic species may comprise a complex catalystmixture, in their monomeric, dimeric or higher nuclearity forms, whichare preferably characterized by at least one phosphorus-containingmolecule complexed per metal, e.g., rhodium. As noted above, it isconsidered that the catalytic species of the preferred catalyst employedin the hydroformylation reaction may be complexed with carbon monoxideand hydrogen in addition to the organophosphorus ligands in view of thecarbon monoxide and hydrogen gas employed by the hydroformylationreaction.

Among the organophosphines that may serve as the ligand of themetal-organophosphine complex catalyst and/or free organophosphineligand of the hydroformylation reaction mixture starting materials aretriorganophosphines, trialkylphosphines, alkyldiarylphosphines,dialkylarylphosphines, dicycloalkylarylphosphines,cycloalkyldiarylphosphines, triaralkylphosphines,tricycloalkylphosphines, and triarylphosphines, alkyl and/or aryldiphosphines and bisphosphine mono oxides, as well as ionictriorganophosphines containing at least one ionic moiety selected fromthe salts of sulfonic acid, of carboxylic acid, of phosphonic acid andof quaternary ammonium compounds, and the like. Of course any of thehydrocarbon radicals of such tertiary non-ionic and ionicorganophosphines may be substituted if desired, with any suitablesubstitutent that does not unduly adversely affect the desired result ofthe hydroformylation reaction. The organophosphine ligands employable inthe hydroformylation reaction andlor methods for their preparation areknown in the art.

Illustrative triorganophosphine ligands may be represented by theformula: ##STR1## wherein each R¹ is the same or different and is asubstituted or unsubstituted monovalent hydrocarbon radical, e.g., analkyl or aryl radical. Suitable hydrocarbon radicals may contain from 1to 24 carbon atoms or greater. Illustrative substituent groups that maybe present on the aryl radicals include, e.g., alkyl radicals, alkoxyradicals, silyl radicals such as --Si(R²)₃ ; amino radicals such as--N(R²)₂ ; acyl radicals such as --C(O)R² ; carboxy radicals such as--C(O)OR² ; acyloxy radicals such as --OC(O)R² ; amido radicals such as--C(O)N(R²)₂ and --N(R²)C(O)R² ; ionic radicals such as --SO₃ M whereinM represents inorganic or organic cationic atoms or radicals; sulfonylradicals such as --SO₂ R² ; ether radicals such as --OR² ; sulfinylradicals such as --SOR² ; sulfenyl radicals such as --SR² as well ashalogen, nitro, cyano, trifluoromethyl and hydroxy radicals, and thelike, wherein each R² individually represents the same or differentsubstituted or unsubstituted monovalent hydrocarbon radical, with theproviso that in amino substituents such as --N(R²)₂, each R² takentogether can also represent a divalent bridging group that forms aheterocyclic radical with the nitrogen atom and in amido substituentssuch as C(O)N(R²)₂ and --N(R²)C(O)R² each --R² bonded to N can also behydrogen. Illustrative alkyl radicals include, e.g., methyl, ethyl,propyl, butyl and the like. Illustrative aryl radicals include, e.g.,phenyl, naphthyl, diphenyl, fluorophenyl, difluorophenyl,benzoyloxyphenyl, carboethoxyphenyl, acetylphenyl, ethoxyphenyl,phenoxyphenyl, hydroxyphenyl; carboxyphenyl, trifluoromethylphenyl,methoxyethylphenyl, acetamidophenyl, dimethylcarbamylphenyl, tolyl,xylyl, and the like.

Illustrative specific organophosphines include, e.g.,triphenylphosphine, tris-p-tolyl phosphine,tris-p-methoxyphenylphosphine, tris-p-fluorophenylphosphine,tris-p-chlorophenylphosphine, tris-dimethylaminophenylphosphine,propyldiphenylphosphine, t-butyldiphenylphosphine,n-butyldiphenylphosphine, n-hexyldiphenylphosphine,cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine,tricyclohexylphosphine, tribenzylphosphine, DIOP, i.e.,(4R,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneand/or(4S,5S)-(+)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneand/or(4S,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,substituted or unsubstituted bicyclic bisphosphines such as1,2-bis(1,4-cyclooctylenephosphino)ethane,1,3-bis(1,4-cyclooctylenephosphino)propane,1,3-bis(1,5-cyclooctylenephosphino)propane and1,2-bis(2,6-dimethyl-1,4-cyclooctylenephosphino)ethane, substituted orunsubstituted bis(2,2'-diphenylphosphinomethyl)biphenyl such asbis(2,2'-diphenylphosphinomethyl)biphenyl andbis{2,2'-di(4-fluorophenyl)phosphinomethyl}biphenyl, xantphos,thixantphos, bis(diphenylphosphino)ferrocene,bis(diisopropylphosphino)ferrocene, bis(diphenylphosphino)ruthenocene,as well as the alkali and alkaline earth metal salts of sulfonatedtriphenylphosphines, e.g., of (tri-m-sulfophenyl)phosphine and of(m-sulfophenyl)diphenyl-phosphine and the like.

More particularly, illustrative metal-organophosphine complex catalystsand illustrative free organophosphine ligands include, e.g., thosedisclosed in U.S. Pat. Nos. 3,527,809; 4,148,830; 4,247,486; 4,283,562;4,400,548; 4,482,749, 4,861,918; 4,694,109; 4,742,178; 4,851,581;4,824,977; 5,332,846; 4,774,362; and WO Patent Application No. 95/30680,published Nov. 16, 1995; the disclosures of which are incorporatedherein by reference.

The organophosphites that may serve as the ligand of themetal-organophosphite ligand complex catalyst and/or free ligand of theprocesses and reaction product mixtures of this invention may be of theachiral (optically inactive) or chiral (optically active) type and arewell known in the art.

Among the organophosphites that may serve as the ligand of themetal-organophosphite complex catalyst and/or free organophosphiteligand of the hydroformylation reaction mixture starting materials aremonoorganophosphites, diorganophosphites, triorganophosphites andorganopolyphosphites. The organophosphite ligands employable in thisinvention and/or methods for their preparation are known in the art.

Representative monoorganophosphites may include those having theformula: ##STR2## wherein R³ represents a substituted or unsubstitutedtrivalent hydrocarbon radical containing from 4 to 40 carbon atoms orgreater, such as trivalent acyclic and trivalent cyclic radicals, e.g.,trivalent alkylene radicals such as those derived from1,2,2-trimethylolpropane and the like, or trivalent cycloalkyleneradicals such as those derived from 1,3,5-trihydroxycyclohexane, and thelike. Such monoorganophosphites may be found described in greaterdetail, e.g., in U.S. Pat. No. 4,567,306, the disclosure of which isincorporated herein by reference.

Representative diorganophosphites may include those having the formula:##STR3## wherein R⁴ represents a substituted or unsubstituted divalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater andW represents a substituted or unsubstituted monovalent hydrocarbonradical containing from 1 to 18 carbon atoms or greater.

Representative substituted and unsubstituted monovalent hydrocarbonradicals represented by W in the above formula (III) include alkyl andaryl radicals, while representative substituted and unsubstituteddivalent hydrocarbon radicals represented by R⁴ include divalent acyclicradicals and divalent aromatic radicals. Illustrative divalent acyclicradicals include, e.g., alkylene, alkylene-oxy-alkylene,alkylene-NX-alkylene wherein X is hydrogen or a substituted orunsubstituted monovalent hydrocarbon radical, alkylene-S-alkylene, andcycloalkylene radicals, and the like. The more preferred divalentacyclic radicals are the divalent alkylene radicals such as disclosedmore fully, e.g., in U.S. Pat. Nos. 3,415,906 and 4,567,302 and thelike, the disclosures of which are incorporated herein by reference.Illustrative divalent aromatic radicals include, e.g., arylene,bisarylene, arylene-alkylene, arylene-alkylene-arylene,arylene-oxy-arylene, arylene-NX-arylene wherein X is as defined above,arylene-S-arylene, and arylene-S-alkylene, and the like. More preferablyR⁴ is a divalent aromatic radical such as disclosed more fully, e.g., inU.S. Pat. Nos. 4,599,206 and 4,717,775, and the like, the disclosures ofwhich are incorporated herein by reference.

Representative of a more preferred class of diorganophosphites are thoseof the formula: ##STR4## wherein W is as defined above, each Ar is thesame or different and represents a substituted or unsubstituted arylradical, each y is the same or different and is a value of 0 or 1, Qrepresents a divalent bridging group selected from --C(R⁵)₂ --, --O--,--S--, --NR⁶⁻, Si(R⁷)₂ -- and --CO--, wherein each R⁵ is the same ordifferent and represents hydrogen, alkyl radicals having from 1 to 12carbon atoms, phenyl, tolyl, and anisyl, R⁶ represents hydrogen or amethyl radical, each R⁷ is the same or different and represents hydrogenor a methyl radical, and m is a value of 0 or 1. Such diorganophosphitesare described in greater detail, e.g., in U.S. Pat. Nos. 4,599,206 and4,717,775, the disclosures of which are incorporated herein byreference.

Representative triorganophosphites may include those having the formula:##STR5## wherein each R⁸ is the same or different and is a substitutedor unsubstituted monovalent hydrocarbon radical, e.g., an alkyl or arylradical. Suitable hydrocarbon radicals may contain from 1 to 24 carbonatoms or greater and may include those described above for R¹ in formula(I).

Representative organopolyphosphites contain two or more tertiary(trivalent) phosphorus atoms and may include those having the formula:##STR6## wherein X¹ represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁹ is the same or different and is a divalent hydrocarbon radicalcontaining from 4 to 40 carbon atoms, each R¹⁰ is the same or differentand is a substituted or unsubstituted monovalent hydrocarbon radicalcontaining from 1 to 24 carbon atoms, a and b can be the same ordifferent and each have a value of 0 to 6, with the proviso that the sumof a+b is 2 to 6 and n equals a+b. Of course it is to be understood thatwhen a has a value of 2 or more, each R⁹ radical may be the same ordifferent, and when b has a value of 1 or more, each R¹⁰ radical mayalso be the same or different.

Representative n-valent (preferably divalent) hydrocarbon bridgingradicals represented by X¹, as well as representative divalenthydrocarbon radicals represented by R⁹ above, include both acyclicradicals and aromatic radicals, such as alkylene, alkylene-Q_(m)-alkylene, cycloalkylene, arylene, bisarylene, arylene-alkylene, andarylene-(CH₂)_(y) --Q_(m) --(CH₂)_(y) -arylene radicals, and the like,wherein Q, m and y are as defined above for formula (IV). The morepreferred acyclic radicals represented by X¹ and R⁹ above are divalentalkylene radicals, while the more preferred aromatic radicalsrepresented by X¹ and R⁹ above are divalent arylene and bisaryleneradicals, such as disclosed more fully, e.g., in U.S. Pat. Nos.3,415,906; 4,567,306; 4,599,206; 4,769,498; 4,717,775; 4,885,401;5,202,297; 5,264,616 and 5,364,950, and the like, the disclosures ofwhich are incorporated herein by reference. Representative monovalenthydrocarbon radicals represented by each R¹⁰ radical above include alkyland aromatic radicals.

Illustrative preferred organopolyphosphites may include bisphosphitessuch as those of formulas (VII) to (IX) below: ##STR7## wherein each R⁹,R¹⁰ and X¹ of formulas (VII) to (IX) are the same as defined above forformula (VI). Preferably, each R⁹ and X¹ represents a divalenthydrocarbon radical selected from alkylene, arylene,arylene-alkylene-arylene, and bisarylene, while each R¹⁰ represents amonovalent hydrocarbon radical selected from alkyl and aryl radicals.Phosphite ligands of such formulas (VI) to (IX) may be found disclosed,e.g., in said U.S. Pat. Nos. 4,668,651; 4,748,261; 4,769,498; 4,885,401;5,202,297; 5,235,113; 5,254,741; 5,264,616; 5,312,996; 5,364,950; and5,391,801; the disclosures of all of which are incorporated herein byreference.

Representative of more preferred classes of organobisphosphites arethose of the following formulas (X) to (XII): ##STR8## wherein Ar, Q,R⁹, R¹⁰, X¹, m and y are as defined above. Most preferably X¹ representsa divalent aryl-(CH₂)_(y) --(Q)_(m) --(CH₂)_(y) -aryl radical whereineach y individually has a value of 0 or 1; m has a value of 0 or 1 and Qis --O--, --S-- or --C(R⁵)₂ -- wherein each R⁵ is the same or differentand represents a hydrogen or methyl radical. More preferably each alkylradical of the above defined R¹⁰ groups may contain from 1 to 24 carbonatoms and each aryl radical of the above-defined Ar, X¹, R⁹ and R¹⁰groups of the above formulas (VI) to (XII) may contain from 6 to 18carbon atoms and said radicals may be the same or different, while thepreferred alkylene radicals of X¹ may contain from 2 to 18 carbon atomsand the preferred alkylene radicals of R⁹ may contain from 5 to 18carbon atoms. In addition, preferably the divalent Ar radicals anddivalent aryl radicals of X¹ of the above formulas are phenyleneradicals in which the bridging group represented by --(CH₂)_(y)--(Q)_(m) --(CH₂)_(y) -- is bonded to said phenylene radicals inpositions that are ortho to the oxygen atoms of the formulas thatconnect the phenylene radicals to their phosphorus atom of the formulas.It is also preferred that any substituent radical when present on suchphenylene radicals be bonded in the para and/or ortho position of thephenylene radicals in relation to the oxygen atom that bonds the givensubstituted phenylene radical to its phosphorus atom.

Moreover, if desired any given organophosphite in the above formulas(VI) to (XII) may be an ionic phosphite, i.e., may contain one or moreionic moieties selected from the group consisting of:

SO₃ M wherein M represents inorganic or organic cation,

PO₃ M wherein M represents inorganic or organic cation,

N(R¹¹)₃ X² wherein each R¹¹ is the same or different and represents ahydrocarbon radical containing from 1 to 30 carbon atoms, e.g, alkyl,aryl, alkaryl, aralkyl, and cycloalkyl radicals, and X² representsinorganic or organic anion,

CO₂ M wherein M represents inorganic or organic cation,

as described, e.g., in U.S. Pat. Nos. 5,059,710; 5,113,022, 5,114,473and 5,449,653, the disclosures of which are incorporated herein byreference. Thus, if desired, such phosphite ligands may contain from 1to 3 such ionic moieties, while it is preferred that only one such ionicmoiety be substituted on any given aryl moiety in the phosphite ligandwhen the ligand contains more than one such ionic moiety. As suitablecounter-ions, M and X², for the anionic moieties of the ionic phosphitesthere can be mentioned hydrogen (i.e. a proton), the cations of thealkali and alkaline earth metals, e.g., lithium, sodium, potassium,cesium, rubidium, calcium, barium, magnesium and strontium, the ammoniumcation, quaternary ammonium cations, phosphonium cations, arsoniumcations and iminium cations. Suitable anionic groups include, forexample, sulfate, carbonate, phosphate, chloride, acetate, oxalate andthe like.

Of course any of the R⁹, R¹⁰, X² and Ar radicals of such non-ionic andionic organophosphites of formulas (VI) to (XII) above may besubstituted if desired, with any suitable substituent containing from 1to 30 carbon atoms that does not unduly adversely affect the desiredresult of the hydroformylation reaction. Substituents that may be onsaid radicals in addition of course to corresponding hydrocarbonradicals such as alkyl, aryl, aralkyl, alkaryl and cyclohexylsubstituents, may include for example silyl radicals such as --Si(R¹²)₃; amino radicals such as --N(R¹²)₂ ; phosphine radicals such as-aryl-P(R¹²)₂ ; acyl radicals such as --C(O)R¹² ; acyloxy radicals suchas --C(O)R¹² ; amido radicals such as --CON(R¹²)₂ and --N(R¹²)COR¹² ;sulfonyl radicals such as --SO₂ R¹² ; alkoxy radicals such as --OR¹² ;sulfinyl radicals such as --SOR¹² ; sulfenyl radicals such as --SR¹² ;phosphonyl radicals such as --P(O)(R¹²)₂ ; as well as, halogen, nitro,cyano, trifluoromethyl, hydroxy radicals, and the like, wherein each R¹²radical is the same or different and represents a monovalent hydrocarbonradical having from 1 to 18 carbon atoms (e.g., alkyl, aryl, aralkyl,alkaryl and cyclohexyl radicals), with the proviso that in aminosubstituents such as --N(R¹²)₂ each R¹² taken together can alsorepresent a divalent bridging group that forms a heterocyclic radicalwith the nitrogen atom, and in amido substituents such as --C(O)N(R¹²)₂and --N(R¹²)COR¹² each R¹² bonded to N can also be hydrogen. Of courseit is to be understood that any of the substituted or unsubstitutedhydrocarbon radicals groups that make up a particular givenorganophosphite may be the same or different.

More specifically illustrative substituents include primary, secondaryand tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl,butyl, sec-butyl, t-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, t-amyl,iso-octyl, decyl, octadecyl, and the like; aryl radicals such as phenyl,naphthyl and the like; aralkyl radicals such as benzyl, phenylethyl,triphenylmethyl, and the like; alkaryl radicals such as tolyl, xylyl,and the like; alicyclic radicals such as cyclopentyl, cyclohexyl,1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, and the like; alkoxyradicals such as methoxy, ethoxy, propoxy, t-butoxy, --OCH₂ CH₂ OCH₃,--(OCH₂ CH₂)₂ OCH₃, --(OCH₂ CH₂)₃ OCH₃, and the like; aryloxy radicalssuch as phenoxy and the like; as well as silyl radicals such as--Si(CH₃)₃, --Si(OCH₃)₃, --Si(C₃ H₇)₃, and the like; amino radicals suchas --NH₂, --N(CH₃)₂, --NHCH₃, --NH(C₂ H₅), and the like; arylphosphineradicals such as --P(C₆ H₅)₂, and the like; acyl radicals such as--C(O)CH₃, --C(O)C₂ H₅, --C(O)C₆ H₅, and the like; carbonyloxy radicalssuch as --C(O)OCH₃ and the like; oxycarbonyl radicals such as --O(CO)C₆H₅, and the like; amido radicals such a --CONH₂, --CON(CH₃)₂,--NHC(O)CH₃, and the like; sulfonyl radicals such as --S(O)₂)C₂ H₅ andthe like; sulfinyl radicals such as --S(O)CH₃ and the like; sulfenylradicals such as --SCH₃, --SC₂ H₅, --SC₆ H₅, and the like; phosphonylradicals such as --P(O)(C₆ H₅)₂, --P(O)(CH₃)₂, --P(O)(C₂ H5)₂, P(O)(C₃H₇)₂, --P(O)(C₄ H₉)₂, --P(O)(C₆ H₁₃)₂, --P(O)CH₃ (C₆ H₅), --P(O)(H)(C₆H₅), and the like.

Specific illustrative examples of such organophosphite ligands includethe following:2-t-butyl-4-methoxyphenyl(3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)phosphitehaving the formula: ##STR9##methyl(3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)phosphitehaving the formula: ##STR10## 6,6'- 4,4'-bis(1,1-dimethylethyl)-1,1'-binaphthyl!-2,2'-diyl!bis(oxy)!bis-dibenzo d,f!1,3,2!-dioxaphosphepin having the formula: ##STR11## 6,6'-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy-1,1'-biphenyl!-2,2'-diyl!bis(oxy)!bis-dibenzo d,f! 1,3,2!dioxaphosphepinhaving the formula: ##STR12## 6,6'-3,3',5,5'-tetrakis(1,1-dimethylpropyl)-1,1'-biphenyl!-2,2'-diyl!bis(oxy)!bis-dibenzo d,f! 1,3,2!dioxaphosphepinhaving the formula: ##STR13## 6,6'-3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl!-2,2'-diyl!bis(oxy)!bis-dibenzod,f! 1,3,2!-dioxaphosphepin having the formula: ##STR14## (2R,4R)-di2,2'-(3,3',5,5'-tetrakis-tert-amyl-1,1'-biphenyl)!-2,4-pentyldiphosphitehaving the formula: ##STR15## (2R,4R)-di2,2'-(3,3',5,5'-tetrakis-tert-butyl-1,1'-biphenyl)!-2,4-pentyldiphosphitehaving the formula: ##STR16## (2R,4R)-di2,2'-(3,3'-di-amyl-5,5'-dimethoxy-1,1'-biphenyl)!-2,4-pentyldiphosphitehaving the formula: ##STR17## (2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-dimethyl-1,1'-biphenyl)!-2,4-pentyldiphosphitehaving the formula: ##STR18## (2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-diethoxy-1,1'-biphenyl)!-2,4-pentyldiphosphitehaving the formula: ##STR19## (2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-diethyl-1,1'-biphenyl)!-2,4-pentyldiphosphitehaving the formula: ##STR20## (2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl)!-2,4-pentyldiphosphitehaving the formula: ##STR21## 6- 2'-(4,6-bis(1,1-dimethylethyl)-1,3,2-benzodioxaphosphol-2-yl)oxy!-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxydibenzod,f! 1,3,2! dioxa-phosphepin having the formula: ##STR22## 6- 2'-1,3,2-benzodioxaphosphol-2-yl)oxy!-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxydibenzod,f! 1,3,2!dioxaphosphepin having the formula: ##STR23## 6- 2'-(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)oxy!-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxydibenzod,f! 1,3,2!dioxaphosphepin having the formula: ##STR24## 2'-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxydibenzo d,f!1,3,2!-dioxaphosphepin-6-yl!oxy!-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxyle,1,1'-biphenyl!2-yl bis(4-hexylphenyl)ester of phosphorous acid havingthe formula: ##STR25## 2- 2- 4,8,-bis(1,1-dimethylethyl),2,10-dimethoxydibenzo d,f!1,3,2!dioxophosphepin-6-yl!oxy!-3-(1,1-dimethylethyl)-5-methoxyphenyl!methyl!-4-methoxy,6-(1,1-dimethylethyl)phenyl diphenyl ester of phosphorous acid havingthe formula: ##STR26## 3-methoxy-1,3-cyclohexamethylene tetrakis3,6-bis(1,1-dimethylethyl)-2-naphthalenyl!ester of phosphorous acidhaving the formula: ##STR27## 2,5-bis(1,1-dimethylethyl)-1,4-phenylenetetrakis 2,4-bis(1,1-dimethylethyl)phenyl!ester of phosphorous acidhaving the formula: ##STR28## methylenedi-2,1-phenylene tetrakis2,4-bis(1,1-dimethylethyl)phenyl!ester of phosphorous acid having theformula: ##STR29## 1,1'-biphenyl!-2,2'-diyl tetrakis2-(1,1-dimethylethyl)-4-methoxyphenyl!ester of phosphorous acid havingthe formula: ##STR30##

Still other illustrative organophosphorus ligands useful in thisinvention include those disclosed in U.S. patent application Ser. No.(D-17459-1), filed on an even date herewith, the disclosure of which isincorporated herein by reference.

The metal-ligand complex catalysts employable in this invention may beformed by methods known in the art. The metal-ligand complex catalystsmay be in homogeneous or heterogeneous form. For instance, preformedmetal hydrido-carbonyl-organophosphorus ligand catalysts may be preparedand introduced into the reaction mixture of a hydroformylation process.More preferably, the metal-ligand complex catalysts can be derived froma metal catalyst precursor which may be introduced into the reactionmedium for in situ formation of the active catalyst. For example,rhodium catalyst precursors such as rhodium dicarbonyl acetylacetonate,Rh₂ O₃, Rh₄ (CO)₁₂, Rh₆ (CO)₁₆, Rh(NO₃)₃ and the like may be introducedinto the reaction mixture along with the organophosphorus ligand for thein situ formation of the active catalyst. In a preferred embodiment ofthis invention, rhodium dicarbonyl acetylacetonate is employed as arhodium precursor and reacted in the presence of a solvent with theorganophosphorus ligand to form a catalytic rhodium-organophosphorusligand complex precursor which is introduced into the reactor along withexcess free organophosphorus ligand for the in situ formation of theactive catalyst. In any event, it is sufficient for the purpose of thisinvention that carbon monoxide, hydrogen and organophosphorus compoundare all ligands that are capable of being complexed with the metal andthat an active metal-organophosphorus ligand catalyst is present in thereaction mixture under the conditions used in the hydroformylationreaction.

More particularly, a catalyst precursor composition can be formedconsisting essentially of a solubilized metal-ligand complex precursorcatalyst, an organic solvent and free ligand. Such precursorcompositions may be prepared by forming a solution of a metal startingmaterial, such as a metal oxide, hydride, carbonyl or salt, e.g. anitrate, which may or may not be in complex combination with a ligand asdefined herein. Any suitable metal starting material may be employed,e.g. rhodium dicarbonyl acetylacetonate, Rh₂ O₃, Rh₄ (CO)₁₂, Rh₆ (CO)₁₆,Rh(NO₃)₃, and organophosphorus ligand rhodium carbonyl hydrides.Carbonyl and organophosphorus ligands, if not already complexed with theinitial metal, may be complexed to the metal either prior to or in situduring the hydroformylation process.

By way of illustration, the preferred catalyst precursor composition ofthis invention consists essentially of a solubilized rhodium carbonylorganophosphorus ligand complex precursor catalyst, a solvent and freeorganophosphorus ligand prepared by forming a solution of rhodiumdicarbonyl acetylacetonate, an organic solvent and a ligand as definedherein. The organophosphorus ligand readily replaces one of the carbonylligands of the rhodium acetylacetonate complex precursor at roomtemperature as witnessed by the evolution of carbon monoxide gas. Thissubstitution reaction may be facilitated by heating the solution ifdesired. Any suitable organic solvent in which both the rhodiumdicarbonyl acetylacetonate complex precursor and rhodiumorganophosphorus ligand complex precursor are soluble can be employed.The amounts of rhodium complex catalyst precursor, organic solvent andorganophosphorus ligand, as well as their preferred embodiments presentin such catalyst precursor compositions may obviously correspond tothose amounts employable in the hydroformylation process of thisinvention. Experience has shown that the acetylacetonate ligand of theprecursor catalyst is replaced after the hydroformylation process hasbegun with a different ligand, e.g., hydrogen, carbon monoxide ororganophosphorus ligand, to form the active complex catalyst asexplained above. In a continuous process, the acetylacetone which isfreed from the precursor catalyst under hydroformylation conditions isremoved from the reaction medium with the product aldehyde and thus isin no way detrimental to the hydroformylation process. The use of suchpreferred rhodium complex catalytic precursor compositions provides asimple economical and efficient method for handling the rhodiumprecursor metal and hydroformylation start-up.

Accordingly, the metal-ligand complex catalysts used in the process ofthis invention consists essentially of the metal complexed with carbonmonoxide and a ligand, said ligand being bonded (complexed) to the metalin a chelated and/or non-chelated fashion. Moreover, the terminology"consists essentially of", as used herein, does not exclude, but ratherincludes, hydrogen complexed with the metal, in addition to carbonmonoxide and the ligand. Further, such terminology does not exclude thepossibility of other organic ligands and/or anions that might also becomplexed with the metal. Materials in amounts which unduly adverselypoison or unduly deactivate the catalyst are not desirable and so thecatalyst most desirably is free of contaminants such as metal-boundhalogen (e.g., chlorine, and the like) although such may not beabsolutely necessary. The hydrogen and/or carbonyl ligands of an activemetal-organophosphorus ligand complex catalyst may be present as aresult of being ligands bound to a precursor catalyst and/or as a resultof in situ formation, e.g., due to the hydrogen and carbon monoxidegases employed in hydroformylation process of this invention.

As noted the hydroformylation reactions involve the use of ametal-ligand complex catalyst as described herein. Of course mixtures ofsuch catalysts can also be employed if desired. Mixtures ofhydroformylation catalysts and hydrogenation catalysts described belowmay also be employed if desired. The amount of metal-ligand complexcatalyst present in the reaction medium of a given hydroformylationreaction need only be that minimum amount necessary to provide the givenmetal concentration desired to be employed and which will furnish thebasis for at least the catalytic amount of metal necessary to catalyzethe particular hydroformylation reaction involved such as disclosed e.g.in the above-mentioned patents. In general, the catalyst concentrationcan range from several parts per million to several percent by weight.Organophosphorus ligands can be employed in the above-mentionedcatalysts in a molar ratio of generally from about 0.5:1 or less toabout 1000:1 or greater. The catalyst concentration will be dependent onthe hydroformylation reaction conditions and solvent employed.

In general, the organophosphorus ligand concentration inhydroformylation reaction mixtures may range from between about 0.005and 25 weight percent based on the total weight of the reaction mixture.Preferably the ligand concentration is between 0.01 and 15 weightpercent, and more preferably is between about 0.05 and 10 weight percenton that basis.

In general, the concentration of the metal in the hydroformylationreaction mixtures may be as high as about 2000 parts per million byweight or greater based on the weight of the reaction mixture.Preferably the metal concentration is between about 50 and 1000 partsper million by weight based on the weight of the reaction mixture, andmore preferably is between about 70 and 800 parts per million by weightbased on the weight of the reaction mixture.

In addition to the metal-ligand complex catalyst, free ligand (i.e.,ligand that is not complexed with the rhodium metal) may also be presentin the hydroformylation reaction medium. The free ligand may correspondto any of the above-defined ligands discussed above as employableherein. It is preferred that the free ligand be the same as the ligandof the metal-ligand complex catalyst employed. However, such ligandsneed not be the same in any given process. The hydroformylation reactionmay involve up to 100 moles, or higher, of free ligand per mole of metalin the hydroformylation reaction medium. Preferably the hydroformylationreaction is carried out in the presence of from about 0.25 to about 50moles of coordinatable phosphorus, and more preferably from about 0.5 toabout 30 moles of coordinatable phosphorus, per mole of metal present inthe reaction medium; said amounts of coordinatable phosphorus being thesum of both the amount of coordinatable phosphorus that is bound(complexed) to the rhodium metal present and the amount of free(non-complexed) coordinatable phosphorus present. Of course, if desired,make-up or additional coordinatable phosphorus can be supplied to thereaction medium of the hydroformylation reaction at any time and in anysuitable manner, e.g. to maintain a predetermined level of free ligandin the reaction medium.

As indicated above, the hydroformylation catalyst may be inheterogeneous form during the reaction and/or during the productseparation. Such catalysts are particularly advantageous in thehydroformylation of olefins or alkadienes to produce high boiling orthermally sensitive aldehydes, so that the catalyst may be separatedfrom the products by filtration or decantation at low temperatures. Forexample, the rhodium catalyst may be attached to a support so that thecatalyst retains its solid form during both the hydroformylation andseparation stages, or is soluble in a liquid reaction medium at hightemperatures and then is precipitated on cooling.

As an illustration, the rhodium catalyst may be impregnated onto anysolid support, such as inorganic oxides, (e.g., alumina, silica,titania, or zirconia) carbon, or ion exchange resins. The catalyst maybe supported on, or intercalated inside the pores of, a zeolite orglass; the catalyst may also be dissolved in a liquid film coating thepores of said zeolite or glass. Such zeolite-supported catalysts areparticularly advantageous for producing one or more regioisomericaldehydes in high selectivity, as determined by the pore size of thezeolite. The techniques for supporting catalysts on solids, such asincipient wetness, which will be known to those skilled in the art. Thesolid catalyst thus formed may still be complexed with one or more ofthe ligands defined above. Descriptions of such solid catalysts may befound in for example: J. Mol. Cat. 1991, 70, 363-368; Catal. Lett. 1991,8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339,454-455; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259.

The rhodium catalyst may be attached to a thin film or membrane support,such as cellulose acetate or polyphenylenesulfone, as described in forexample J. Mol. Cat. 1990, 63, 213-221.

The rhodium catalyst may be attached to an insoluble polymeric supportthrough an organophosphorus-containing ligand, such as a phosphine orphosphite, incorporated into the polymer. Such polymer-supported ligandsare well known, and include such commercially available species as thedivinylbenzene/polystyrene-supported triphenylphosphine. The supportedligand is not limited by the choice of polymer or phosphorus-containingspecies incorporated into it. Descriptions of polymer-supportedcatalysts may be found in for example: J. Mol. Cat. 1993, 83, 17-35;Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 7122-7127.

In the heterogeneous catalysts described above, the catalyst may remainin its heterogeneous form during the entire hydroformylation andcatalyst separation process. In another embodiment of the invention, thecatalyst may be supported on a polymer which, by the nature of itsmolecular weight, is soluble in the reaction medium at elevatedtemperatures, but precipitates upon cooling, thus facilitating catalystseparation from the reaction mixture. Such "soluble" polymer-supportedcatalysts are described in for example: Polymer, 1992, 33, 161; J. Org.Chem. 1989, 54, 2726-2730.

When the rhodium catalyst is in a heterogeneous or supported form, thereaction may be carried out in the gas phase. More preferably, thereaction is carried out in the slurry phase due to the high boilingpoints of the products, and to avoid decomposition of the productaldehydes. The catalyst may then be separated from the product mixtureby filtration or decantation.

The substituted and unsubstituted alkadiene starting materials useful inthe hydroformylation reactions include, but are not limited to,conjugated aliphatic diolefins represented by the formula: ##STR31##wherein R₁ and R₂ are the same or different and are hydrogen, halogen ora substituted or unsubstituted hydrocarbon radical. The alkadienes canbe linear or branched and can contain substituents (e.g., alkyl groups,halogen atoms, amino groups or silyl groups). Illustrative of suitablealkadiene starting materials are butadiene, isoprene, dimethyl butadieneand cyclopentadiene. Most preferably, the alkadiene starting material isbutadiene itself (CH₂ ═CH--CH═CH₂). For purposes of this invention, theterm "alkadiene" is contemplated to include all permissible substitutedand unsubstituted conjugated diolefins, including all permissiblemixtures comprising one or more substituted or unsubstituted conjugateddiolefins. Illustrative of suitable substituted and unsubstitutedalkadienes (including derivatives of alkadienes) include thosepermissible substituted and unsubstituted alkadienes described inKirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996,the pertinent portions of which are incorporated herein by reference.

The hydroformylation reaction conditions may include any suitable typehydroformylation conditions heretofore employed for producing aldehydes.For instance, the total gas pressure of hydrogen, carbon monoxide andolefin or alkadiene starting compound of the hydroformylation processmay range from about 1 to about 10,000 psia. In general, thehydroformylation process is operated at a total gas pressure ofhydrogen, carbon monoxide and olefin or alkadiene starting compound ofless than about 1500 psia and more preferably less than about 1000 psia,the minimum total pressure being limited predominately by the amount ofreactants necessary to obtain a desired rate of reaction. The totalpressure employed in the hydroformylation reaction may range in generalfrom about 20 to about 3000 psia, preferably from about 50 to 1500 psia.The total pressure of the hydroformylation process will be dependent onthe particular catalyst system employed.

More specifically, the carbon monoxide partial pressure of thehydroformylation process in general may range from about 1 to about 3000psia, and preferably from about 3 to about 1500 psia, while the hydrogenpartial pressure in general may range from about 1 to about 3000 psia,and preferably from about 3 to about 1500 psia. In general, the molarratio of carbon monoxide to gaseous hydrogen may range from about 100:1or greater to about 1:100 or less, the preferred carbon monoxide togaseous hydrogen molar ratio being from about 1:10 to about 10:1. Thecarbon monoxide and hydrogen partial pressures will be dependent in parton the particular catalyst system employed.

Carbon monoxide partial pressure should be sufficient for thehydroformylation reaction, e.g., of an alkadiene to pentenal, to occurat an acceptable rate. Hydrogen partial pressure must be sufficient forthe hydroformylation and/or hydrogenation reaction to occur at anacceptable rate, but not so high that hydrogenation of butadiene orisomerization of pentenals to undesired isomers occurs. It is understoodthat carbon monoxide and hydrogen can be employed separately, in mixturewith each other, i.e., synthesis gas, or may in part be produced in situunder reaction conditions.

Further, the hydroformylation process may be conducted at a reactiontemperature from about 20° C. to about 200° C. may be employed,preferably from about 50° C. to about 150° C., and more preferably fromabout 65° C. to about 115° C. The temperature must be sufficient forreaction to occur (which may vary with catalyst system employed), butnot so high that ligand or catalyst decomposition occurs. At hightemperatures (which may vary with catalyst system employed),isomerization of pentenals to undesired isomers may occur.

Of course, it is to be also understood that the hydroformylationreaction conditions employed will be governed by the type of aldehydeproduct desired.

In the alkadiene hydroformylation step, the alkadiene hydroformylationreaction may be conducted at an alkadiene conversion and/or carbonmonoxide partial pressure sufficient to selectively produce thepentenals and penten-1-ols respectively. In certain cases, it has beenfound that if the partial pressure of carbon monoxide in the alkadienehydroformylation reaction system is higher than the partial pressure ofhydrogen, the conversion of pentenal intermediates to hydrogenated andbishydroformylated byproducts is suppressed. It is believed that thesereactions are inhibited by carbon monoxide. It has also been found thatwhen the alkadiene hydroformylation reaction is conducted withincomplete conversion of butadiene, the conversion of pentenalintermediates to bishydroformylated byproducts is suppressed. Ingeneral, the alkadiene conversion can range from about 1 weight percentto about 100 weight percent, preferably from about 10 weight percent toabout 100 weight percent, and more preferably from about 25 weightpercent to about 100 weight percent, based on the total weight ofalkadiene fed to the reaction. While not wishing to be bound to anyparticular theory, it is believed that butadiene preferentiallycomplexes with the metal-ligand complex catalyst, acting as an inhibitorto the hydroformylation of the pentenal intermediates. The partialconversion of butadiene may be accomplished by short reaction time, lowtotal pressure, low catalyst concentration, and/or low temperature. Highbutadiene concentrations are especially useful in the hydroformylationprocesses of this invention.

In the penten-1-ol reductive hydroformylation step of this invention,the penten-1-ol reductive hydroformylation reaction can be conducted ata penten-1-ol conversion and/or carbon monoxide partial pressuresufficient to selectively produce the 1,6-hexanediols. However, in thepenten-1-ol reductive hydroformylation reaction, the penten-1-olconversion may be complete or incomplete, and the partial pressure ofcarbon monoxide may be higher or lower than the partial pressure ofhydrogen as described above.

To enable maximum levels of 3-pentenals and/or 4-pentenals and minimize2-pentenals, it is desirable to maintain some alkadiene partialpressure, or when the alkadiene conversion is complete, the carbonmonoxide partial pressure should be sufficient to prevent or minimizederivatization, e.g., isomerization and/or hydrogenation, of substitutedor unsubstituted 3-pentenals.

In an embodiment, the alkadiene hydroformylation is conducted at analkadiene partial pressure and/or a carbon monoxide partial pressuresufficient to prevent or minimize derivatization, e.g., isomerizationand/or hydrogenation, of substituted or unsubstituted 3-pentenals. Inanother embodiment, the alkadiene, e.g., butadiene, hydroformylation isconducted at an alkadiene partial pressure of greater than 0 psi,preferably greater than 5 psi, and more preferably greater than 9 psi;and at a carbon monoxide partial pressure of greater than 0 psi,preferably greater than 25 psi, and more preferably greater than 100psi.

The hydroformylation reaction is also conducted in the presence of wateror an organic solvent for the metal-ligand complex catalyst and freeligand. Depending on the particular catalyst and reactants employed,suitable organic solvents include, for example, alcohols, alkanes,alkenes, alkynes, ethers, aldehydes, higher boiling aldehydecondensation byproducts, ketones, esters, amides, tertiary amines,aromatics and the like. Any suitable solvent which does not undulyadversely interfere with the intended hydroformylation reaction can beemployed and such solvents may include those disclosed heretoforecommonly employed in known metal catalyzed hydroformylation reactions.Mixtures of one or more different solvents may be employed if desired.In general, with regard to the production of aldehydes, it is preferredto employ aldehyde compounds corresponding to the aldehyde productsdesired to be produced and/or higher boiling aldehyde liquidcondensation byproducts as the main organic solvents as is common in theart. Such aldehyde condensation byproducts can also be preformed ifdesired and used accordingly. Illustrative preferred solvents employablein the production of aldehydes include ketones (e.g. acetone andmethylethyl ketone), esters (e.g. ethyl acetate), hydrocarbons (e.g.toluene), nitrohydrocarbons (e.g. nitrobenzene), ethers (e.g.tetrahydrofuran (THF) and glyme), 1,4-butanediols and sulfolane.Suitable solvents are disclosed in U.S. Pat. No. 5,312,996. The amountof solvent employed is not critical to the subject invention and needonly be that amount sufficient to solubilize the catalyst and freeligand of the hydroformylation reaction mixture to be treated. Ingeneral, the amount of solvent may range from about 5 percent by weightup to about 99 percent by weight or more based on the total weight ofthe hydroformylation reaction mixture starting material.

The reductive hydroformylation process may also be conducted in thepresence of a promoter. As used herein, "promoter" means an organic orinorganic compound with an ionizable hydrogen of pKa of from about 1 toabout 35. Illustrative promoters include, for example, protic solvents,organic and inorganic acids, alcohols, water, phenols, thiols,thiophenols, nitroalkanes, ketones, nitriles, amines (e.g., pyrroles anddiphenylamine), amides (e.g., acetamide), mono-, di- andtrialkylammonium salts, and the like. The promoter may be present in thereductive hydroformylation reaction mixture either alone or incorporatedinto the ligand structure, either as the metal-ligand complex catalystor as free ligand, or into the alkadiene structure. The desired promoterwill depend on the nature of the ligands and metal of the metal-ligandcomplex catalysts. In general, a catalyst with a more basic metal-boundacyl or other intermediate will require a lower concentration and/or aless acidic promoter. In general, the amount of promoter may range fromabout 10 parts per million or so up to about 99 percent by weight ormore based on the total weight of the reductive hydroformylation processmixture starting materials.

In an embodiment of the invention, the hydroformylation reaction mixturemay consist of one or more liquid phases, e.g. a polar and a nonpolarphase. Such processes are often advantageous in, for example, separatingproducts from catalyst and/or reactants by partitioning into eitherphase. In addition, product selectivities dependent upon solventproperties may be increased by carrying out the reaction in thatsolvent. A well-known application of this technology is theaqueous-phase hydroformylation of olefins employing sulfonated phosphineligands for the rhodium catalyst. A process carried out in aqueoussolvent is particularly advantageous for the preparation of aldehydesbecause the products may be separated from the catalyst by extractioninto an organic solvent. Alternatively, aldehydes, particularlypentenals, adipaldehyde and 6-hydroxyhexanal, which tend to undergoself-condensation reactions, are expected to be stabilized in aqueoussolution as the aldehyde hydrates.

As described herein, the phosphorus-containing ligand for the rhodiumhydroformylation catalyst may contain any of a number of substituents,such as cationic or anionic substituents, which will render the catalystsoluble in a polar phase, e.g. water. Optionally, a phase-transfercatalyst may be added to the reaction mixture to facilitate transport ofthe catalyst, reactants, or products into the desired solvent phase. Thestructure of the ligand or the phase-transfer catalyst is not criticaland will depend on the choice of conditions, reaction solvent, anddesired products.

When the catalyst is present in a multiphasic system, the catalyst maybe separated from the reactants and/or products by conventional methodssuch as extraction or decantation. The reaction mixture itself mayconsist of one or more phases; alternatively, the multiphasic system maybe created at the end of the reaction by for example addition of asecond solvent to separate the products from the catalyst. See, forexample, U.S. Pat. No. 5,180,854, the disclosure of which isincorporated herein by reference.

In an embodiment of the process of this invention, an olefin can behydroformylated along with a alkadiene using the above-describedmetal-ligand complex catalysts. In such cases, an aldehyde derivative ofthe olefin is also produced along with the pentenals. It has been foundthat the alkadiene reacts to form a complex with the metal more rapidlythan certain of the olefins and requires more forcing conditions to behydroformylated itself than certain of the olefins.

Mixtures of different olefinic starting materials can be employed, ifdesired, in the hydroformylation reactions. More preferably thehydroformylation reactions are especially useful for the production ofpentenals, by hydroformylating alkadienes in the presence of alphaolefins containing from 2 to 30, preferably 4 to 20, carbon atoms,including isobutylene, and internal olefins containing from 4 to 20carbon atoms as well as starting material mixtures of such alpha olefinsand internal olefins. Commercial alpha olefins containing four or morecarbon atoms may contain minor amounts of corresponding internal olefinsand/or their corresponding saturated hydrocarbon and that suchcommercial olefins need not necessarily be purified from same prior tobeing hydroformylated.

Illustrative of other olefinic starting materials include alpha-olefins,internal olefins, 1,3-dienes, alkyl alkenoates, alkenyl alkanoates,alkenyl alkyl ethers, alkenols, alkenals, and the like, e.g., ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,2-butene, 2-methyl propene (isobutylene), 2-methylbutene, 2-pentene,2-hexene, 3-hexane, 2-heptene, cyclohexene, propylene dimers, propylenetrimers, propylene tetramers, piperylene, isoprene, 2-ethyl-1-hexene,2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene,3-cyclohexyl-1-butene, allyl alcohol, allyl butyrate, hex-1-en-4-ol,oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinylpropionate, allyl propionate, methyl methacrylate, vinyl ethyl ether,vinyl methyl ether, vinyl cyclohexene, allyl ethyl ether, methylpentenoate, n-propyl-7-octenoate, pentenals, e.g., 2-pentenal,3-pentenal and 4-pentenal; penten-1-ols, e.g., 2-penten-1-ol,3-penten-1-ol and 4-penten-1-ol; 3-butenenitrile, 3-pentenenitrile,5-hexenamide, 4-methyl styrene, 4-isopropyl styrene, 4-tert-butylstyrene, alpha-methyl styrene, 4-tert-butyl-alpha-methyl styrene,1,3-diisopropenylbenzene, eugenol, iso-eugenol, safrole, iso-safrole,anethol, 4-allylanisole, indene, limonene, beta-pinene,dicyclopentadiene, cyclooctadiene, camphene, linalool, and the like.Other illustrative olefinic compounds may include, for example,p-isobutylstyrene, 2-vinyl-6-methoxynaphthylene, 3-ethenylphenyl phenylketone, 4-ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl,4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)styrene,2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether,propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and thelike. Other olefinic compounds include substituted aryl ethylenes asdescribed in U.S. Pat. No. 4,329,507, the disclosure of which isincorporated herein by reference.

As indicated above, it is generally preferred to carry out thehydroformylation process of this invention in a continuous manner. Ingeneral, continuous hydroformylation processes are well known in the artand may involve: (a) hydroformylating the olefinic or alkadiene startingmaterial(s) with carbon monoxide and hydrogen in a liquid homogeneousreaction mixture comprising a solvent, the metal-ligand complexcatalyst, and free ligand; (b) maintaining reaction temperature andpressure conditions favorable to the hydroformylation of the olefinic oralkadiene starting material(s); (c) supplying make-up quantities of theolefinic or alkadiene starting material(s), carbon monoxide and hydrogento the reaction medium as those reactants are used up; and (d)recovering the desired aldehyde hydroformylation product(s) in anymanner desired. The continuous process can be carried out in a singlepass mode, i.e., wherein a vaporous mixture comprising unreactedolefinic or alkadiene starting materials) and vaporized aldehyde productis removed from the liquid reaction mixture from whence the aldehydeproduct is recovered and make-up olefinic or alkadiene startingmaterial(s), carbon monoxide and hydrogen are supplied to the liquidreaction medium for the next single pass through without recycling theunreacted olefinic or alkadiene starting material(s). However, it isgenerally desirable to employ a continuous process that involves eithera liquid and/or gas recycle procedure. Such types of recycle procedureare well known in the art and may involve the liquid recycling of themetal-ligand complex catalyst solution separated from the desiredaldehyde reaction product(s), such as disclosed e.g., in U.S. Pat.4,148,830 or a gas cycle procedure such as disclosed e.g., in U.S. Pat.4,247,486, as well as a combination of both a liquid and gas recycleprocedure if desired. The disclosures of said U.S. Pat. 4,148,830 and4,247,486 are incorporated herein by reference thereto. The mostpreferred hydroformylation process of this invention comprises acontinuous liquid catalyst recycle process.

Illustrative substituted and unsubstituted pentenal intermediates thatcan be prepared by the processes of this invention include one or moreof the following: cis-2-pentenal, trans-2-pentenal, cis-3-pentenal,trans-3-pentenal, and/or 4-pentenal, including mixtures of one or moreof the above pentenals. Illustrative of suitable substituted andunsubstituted pentenals (including derivatives of pentenals) includethose permissible substituted and unsubstituted pentenals which aredescribed in Kirk-Othmer, Encyclopedia of Chemical Technology, FourthEdition, 1996, the pertinent portions of which are incorporated hereinby reference.

Illustrative substituted and unsubstituted 6-hydroxyhexanal productsthat can be prepared by the processes of this invention include, forexample, 6-hydroxyhexanal and substituted 6-hydroxyhexanals (e.g.,2-methyl-6-hydroxyhexanal and 3,4-dimethyl-6-hydroxyhexanal) and thelike, including mixtures of one or more of the above 6-hydroxyhexanals.Illustrative of suitable substituted and unsubstituted 6-hydroxyhexanals(including derivatives of 6-hydroxyhexanals) include those permissiblesubstituted and unsubstituted 6-hydroxyhexanals which are described inKirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996,the pertinent portions of which are incorporated herein by reference.

As indicated above, the hydroformylation reactions may involve a liquidcatalyst recycle procedure. Such liquid catalyst recycle procedures areknown as seen disclosed, e.g., in U. S. Pat. Nos. 4,668,651; 4,774,361;5,102,505 and 5,110,990. For instance, in such liquid catalyst recycleprocedures it is common place to continuously or intermittently remove aportion of the liquid reaction product medium, containing, e.g., thealdehyde product, the solubilized metal-ligand complex catalyst, freeligand, and organic solvent, as well as byproducts produced in situ bythe hydroformylation, e.g., aldehyde condensation byproducts etc., andunreacted olefinic or alkadiene starting material, carbon monoxide andhydrogen (syn gas) dissolved in said medium, from the hydroformylationreactor, to a distillation zone, e.g., a vaporizer/separator wherein thedesired aldehyde product is distilled in one or more stages undernormal, reduced or elevated pressure, as appropriate, and separated fromthe liquid medium. The vaporized or distilled desired aldehyde productso separated may then be condensed and recovered in any conventionalmanner as discussed above. The remaining non-volatilized liquid residuewhich contains metal-ligand complex catalyst, solvent, free ligand andusually some undistilled aldehyde product is then recycled back, with orwith out further treatment as desired, along with whatever by-productand non-volatilized gaseous reactants that might still also be dissolvedin said recycled liquid residue, in any conventional manner desired, tothe hydroformylation reactor, such as disclosed e.g., in theabove-mentioned patents. Moreover the reactant gases so removed by suchdistillation from the vaporizer may also be recycled back to the reactorif desired.

In an embodiment of this invention, the aldehyde mixtures may beseparated from the other components of the crude reaction mixtures inwhich the aldehyde mixtures are produced by any suitable method.Suitable separation methods include, for example, solvent extraction,crystallization, distillation, vaporization, phase separation, wipedfilm evaporation, falling film evaporation and the like. It may bedesired to remove the aldehyde products from the crude reaction mixtureas they are formed through the use of trapping agents as described inpublished Patent Cooperation Treaty Patent Application WO 88/08835. Amethod for separating the aldehyde mixtures from the other components ofthe crude reaction mixtures is by membrane separation. Such membraneseparation can be achieved as set out in U.S. Pat. No. 5,430,194 andcopending U.S. patent application Ser. No. 08/430,790, filed May 5,1995, both incorporated herein by reference. The subsequenthydrogenation of the aldehyde mixtures may be conducted without the needto separate the aldehydes from the other components of the crudereaction mixtures.

As indicated above, at the conclusion of (or during) the process of thisinvention, the desired pentenals may be recovered from the reactionmixtures used in the process of this invention. For example, therecovery techniques disclosed in U.S. Pat. Nos. 4,148,830 and 4,247,486can be used. For instance, in a continuous liquid catalyst recycleprocess the portion of the liquid reaction mixture (containing pentenalproduct, catalyst, etc.) removed from the reactor can be passed to avaporizer/separator wherein the desired aldehyde product can beseparated via distillation, in one or more stages, under normal, reducedor elevated pressure, from the liquid reaction solution, condensed andcollected in a product receiver, and further purified if desired. Theremaining non-volatilized catalyst containing liquid reaction mixturemay then be recycled back to the reactor as may, if desired, any othervolatile materials, e.g., unreacted olefin or alkadiene, together withany hydrogen and carbon monoxide dissolved in the liquid reaction afterseparation thereof from the condensed pentenal product, e.g., bydistillation in any conventional manner. It is generally desirable toemploy an organophosphorus ligand whose molecular weight exceeds that ofthe higher boiling aldehyde oligomer byproduct corresponding to thepentenals or hydroxyhexanals being produced in the hydroformylationprocess. Another suitable recovery technique is solvent extraction orcrystallization. In general, it is preferred to separate the desiredpentenals or hydroxyhexanals from the catalyst-containing reactionmixture under reduced pressure and at low temperatures so as to avoidpossible degradation of the organophosphorus ligand and reactionproducts. When an alpha-mono-olefin reactant is also employed, thealdehyde derivative thereof can also be separated by the above methods.

More particularly, distillation and separation of the desired aldehydeproduct from the metal-ligand complex catalyst containing productsolution may take place at any suitable temperature desired. In general,it is recommended that such distillation take place at relatively lowtemperatures, such as below 150° C., and more preferably at atemperature in the range of from about 50° C. to about 130° C. It isalso generally recommended that such aldehyde distillation take placeunder reduced pressure, e.g., a total gas pressure that is substantiallylower than the total gas pressure employed during hydroformylation whenlow boiling aldehydes (e.g., C₅ and C₆) are involved or under vacuumwhen high boiling aldehydes (e.g. C7 or greater) are involved. Forinstance, a common practice is to subject the liquid reaction productmedium removed from the hydroformylation reactor to a pressure reductionso as to volatilize a substantial portion of the unreacted gasesdissolved in the liquid medium which now contains a much lower synthesisgas concentration than was present in the hydroformylation reactionmedium to the distillation zone, e.g. vaporizer/separator, wherein thedesired aldehyde product is distilled. In general, distillationpressures ranging from vacuum pressures on up to total gas pressure ofabout 50 psig should be sufficient for most purposes.

Particularly when conducting the process of this invention in acontinuous liquid recycle mode employing an organophosphite ligand,undesirable acidic byproducts (e.g., a hydroxy alkyl phosphonic acid)may result due to reaction of the organophosphite ligand and thealdehydes over the course of the process. The formation of suchbyproducts undesirably lowers the concentration of the ligand. Suchacids are often insoluble in the reaction mixture and such insolubilitycan lead to precipitation of an undesirable gelatinous byproduct and mayalso promote the autocatalytic formation of further acidic byproducts.The organopolyphosphite ligands used in the process of this inventionhave good stability against the formation of such acids. However, ifthis problem does occur, the liquid reaction effluent stream of acontinuous liquid recycle process may be passed, prior to (or morepreferably after) separation of the desired pentenal or hydroxyhexanalproduct therefrom, through any suitable weakly basic anion exchangeresin, such as a bed of amine Amberlyst® resin, e.g., Amberlyst® A-21,and the like, to remove some or all of the undesirable acidic byproductsprior to its reincorporation into the hydroformylation reactor. Ifdesired, more than one such basic anion exchange resin bed, e.g. aseries of such beds, may be employed and any such bed may be easilyremoved and/or replaced as required or desired. Alternatively ifdesired, any part or all of the acid-contaminated catalyst recyclestream may be periodically removed from the continuous recycle operationand the contaminated liquid so removed treated in the same fashion asoutlined above, to eliminate or reduce the amount of acidic by-productprior to reusing the catalyst containing liquid in the hydroformylationprocess. Likewise, any other suitable method for removing such acidicbyproducts from the hydroformylation process of this invention may beemployed herein if desired such as by extraction of the acid with a weakbase (e.g., sodium bicarbonate).

The processes useful in this invention may involve improving thecatalyst stability of any organic solubilizedrhodium-organopolyphosphite complex catalyzed, liquid recyclehydroformylation process directed to producing aldehydes from olefinicunsaturated compounds which may experience deactivation of the catalystdue to recovery of the aldehyde product by vaporization separation froma reaction product solution containing the organic solubilizedrhodium-organopolyphosphite complex catalyst and aldehyde product, theimprovement comprising carrying out said vaporization separation in thepresence of a heterocyclic nitrogen compound. See, for example,copending U.S. patent application Ser. No. 08/756,789, filed Nov. 26,1996, the disclosure of which is incorporated herein by reference.

The processes useful in this invention may involve improving thehydrolytic stability of the organophosphite ligand and thus catalyststability of any organic solubilized rhodium-organophosphite ligandcomplex catalyzed hydroformylation process directed to producingaldehydes from olefinic unsaturated compounds, the improvementcomprising treating at least a portion of an organic solubilizedrhodium-organophosphite ligand complex catalyst solution derived fromsaid process and which also contains phosphorus acidic compounds formedduring the hydroformylation process, with an aqueous buffer solution inorder to neutralize and remove at least some amount of said phosphorusacidic compounds from said catalyst solution, and then returning thetreated catalyst solution to the hydroformylation reactor. See, forexample, copending U.S. patent application Ser. Nos. 08/756,501 and08/753,505, both filed Nov. 26, 1996, the disclosures of which areincorporated herein by reference.

In an embodiment of this invention, deactivation ofmetal-organopolyphosphorus ligand complex catalysts caused by aninhibiting or poisoning organomonophosphorus compound can be reversed orat least minimized by carrying out hydroformylation processes in areaction region where the hydroformylation reaction rate is of anegative or inverse order in carbon monoxide and optionally at one ormore of the following conditions: at a temperature such that thetemperature difference between reaction product fluid temperature andinlet coolant temperature is sufficient to prevent and/or lessen cyclingof carbon monoxide partial pressure, hydrogen partial pressure, totalreaction pressure, hydroformylation reaction rate and/or temperatureduring said hydroformylation process; at a carbon monoxide conversionsufficient to prevent and/or lessen cycling of carbon monoxide partialpressure, hydrogen partial pressure, total reaction pressure,hydroformylation reaction rate and/or temperature during saidhydroformylation process; at a hydrogen conversion sufficient to preventand/or lessen cycling of carbon monoxide partial pressure, hydrogenpartial pressure, total reaction pressure, hydroformylation reactionrate and/or temperature during said hydroformylation process;

and at an olefinic unsaturated compound conversion sufficient to preventand/or lessen cycling of carbon monoxide partial pressure, hydrogenpartial pressure, total reaction pressure, hydroformylation reactionrate and/or temperature during said hydroformylation process. See, forexample, copending U.S. patent application Ser. No. 08/756,499, filedNov. 26, 1996, the disclosure of which is incorporated herein byreference.

Hydrogenation Steps or Stages

The hydrogenation processes may involve converting one or moresubstituted or unsubstituted pentenals to one or more substituted orunsubstituted penten-1-ols. In general, the hydrogenation step or stagecomprises reacting one or more substituted or unsubstituted pentenalswith hydrogen in the presence of a catalyst to produce one or moresubstituted or unsubstituted penten-1-ols.

Illustrative of suitable hydrogenation processes are described, forexample, in U.S. Pat. Nos. 5,004,845, 5,003,110, 4,762,817 and4,876,402, the disclosures of which are incorporated herein byreference. As used herein, the term "hydrogenation" is contemplated toinclude, but is not limited to, all permissible hydrogenation processesincluding those involved with reductive hydroformylation and shallinclude, but are not limited to, converting one or more substituted orunsubstituted pentenals to one or more substituted or unsubstitutedpenten-1-ols.

Pentenals useful in t he hydrogenation process are known materials andcan be prepared by the hydroformylation step described above or by aconventional method. Reaction mixtures comprising pentenals may beuseful herein. The amount of pentenals employed in the hydrogenationstep is not narrowly critical and can be any amount sufficient toproduce penten-1-ols, preferably in high selectivities.

The reactors and reaction conditions for the hydrogenation reaction stepare known in the art. The particular hydrogenation reaction conditionsare not narrowly critical and can be any effective hydrogenationconditions sufficient to produce one or more penten-1-ols. The reactorsmay be stirred tanks, tubular reactors and the like. The exact reactionconditions will be governed by the best compromise between achievinghigh catalyst selectivity, activity, lifetime and ease of operability,as well as the intrinsic reactivity of the starting materials inquestion and the stability of the starting materials and the desiredreaction product to the reaction conditions. Recovery and purificationmay be by any appropriate means, and may include distillation, phaseseparation, extraction, absorption, crystallization, membrane,derivative formation and the like.

The particular hydrogenation reaction conditions are not narrowlycritical and can be any effective hydrogenation procedures sufficient toproduce one or more penten-1-ols. The combination of relatively lowtemperatures and low hydrogen pressures as described below may providegood reaction rates and high product selectivities. The hydrogenationreaction may proceed in the presence of water without substantialdegradation of the hydrogenation catalyst.

The hydrogenation reaction can be conducted at a temperature of fromabout 0° C. to 180° C. for a period of about 1 hour or less to about 12hours or longer with the longer time being used at the lowertemperature, preferably from about 25° C. to about 140° C. for about 1hour or less to about 8 hours or longer, and more preferably at about50° C. to 125° C. for about 1 hour or less to about 3 hours or longer.

The hydrogenation reaction can be conducted over a wide range ofhydrogen pressures ranging from about 50 psig to about 10000 psig,preferably from about 200 psig to about 1500 psig. It is most preferableto conduct the hydrogenation reaction at hydrogen pressures of fromabout 500 psig to about 1000 psig. The reaction is preferably effectedin the liquid or vapor states or mixtures thereof, more preferably inthe liquid state.

Transfer hydrogenation may be used to hydrogenate an aldehyde to analcohol. In this process, the hydrogen required for the reduction of thealdehyde is obtained by dehydrogenation of an alcohol to an aldehyde orketone. Transfer hydrogenation can be catalyzed by a variety ofcatalysts, both homogeneous or heterogeneous. For example, a commoncatalyst is aluminum isopropoxide and a common alcohol is isopropanol.This system has the advantage that the resultant ketone, acetone, isvolatile and can be easily removed from the reaction system byvaporization. Since transfer hydrogenation is generally an equilibriumlimited process, removal of a volatile product can be used to drive thereaction to completion. The acetone produced in such a process may behydrogenated in a separate step and recycled to the transferhydrogenation reaction if desired. Other suitable catalysts for thetransfer hydrogenation reaction include those known heterogeneoushydrogenation and dehydrogenation catalysts described below. Usefulhomogeneous catalysts include, for example, aluminum alkoxides andhalides, zirconium, ruthenium and rhodium.

The hydrogenation reaction can be conducted using known hydrogenationcatalysts in conventional amounts. Illustrative of suitablehydrogenation catalysts include, for example, Raney-type compounds suchas Raney nickel and modified Raney nickels; molybdenum-promoted nickel,chromium-promoted nickel, cobalt-promoted nickel; platinum; palladium;iron; cobalt molybdate on alumina; copper chromite; barium promotedcopper chromite; tin-copper couple; zinc-copper couple; aluminum-cobalt;aluminum-copper; aluminum-nickel; platinum; nickel; cobalt; ruthenium;rhodium; iridium; palladium; rhenium; copper; yttrium on magnesia;lanthanide metals such as lanthanum and cerium; platinum/zinc/iron;platinum/cobalt; Raney cobalt; osmium; and the like. The preferredcatalysts are nickel, platinum, cobalt, rhenium and palladium. Thehydroformylation and hydrogenation reaction conditions may be the sameor different and the hydroformylation and hydrogenation catalysts may bethe same or different. Suitable catalysts useful in both thehydroformylation and hydrogenation reactions include, for example,ligand-free rhodium, phosphine-promoted rhodium, amine-promoted rhodium,cobalt, phosphine-promoted cobalt, ruthenium, and phosphine-promotedpalladium catalysts. Mixtures of hydrogenation catalysts andhydroformylation catalysts described above may be employed if desired.As indicated above, the hydrogenation catalyst may be homogeneous orheterogeneous.

The amount of catalyst used in the hydrogenation reaction is dependenton the particular catalyst employed and can range from about 0.01 weightpercent or less to about 10 weight percent or greater of the totalweight of the starting materials.

Illustrative substituted and unsubstituted penten-1-ol intermediatesthat can be prepared by the processes of this invention include one ormore of the following: cis-2-penten-1-ol, trans-2-penten-1-ol,cis-3-penten-1-ol, trans-3-penten-1-ol, and/or 4-penten-1-ol, includingmixtures comprising one or more of the above penten-1-ols. Illustrativeof suitable substituted and unsubstituted penten-1-ols (includingderivatives of penten-1-ols) include those permissible substituted andunsubstituted penten-1-ols which are described in Kirk-Othmer,Encyclopedia of Chemical Technology, Fourth Edition, 1996, the pertinentportions of which are incorporated herein by reference.

As indicated above, the substituted and unsubstituted penten-1-olsproduced by the hydrogenation step of this invention can be separated byconventional techniques such as distillation, extraction, precipitation,crystallization, membrane separation, phase separation or other suitablemeans. For example, a crude reaction product can be subjected to adistillation-separation at atmospheric or reduced pressure through apacked distillation column. Reactive distillation may be useful inconducting the hydrogenation reaction step.

A one-step process involving the reductive hydroformylation of one ormore substituted or unsubstituted alkadienes to produce one or moresubstituted or unsubstituted 6-hydroxyhexanals is disclosed in copendingU.S. patent application Ser. No. (D-17488-1), filed on an even dateherewith, the disclosure of which is incorporated herein by reference.Another process involving the production of one or more substituted orunsubstituted hydroxyaldehydes by hydrocarbonylation/hydroformylation isdisclosed in copending U.S. patent application Ser. No. (D-17779), filedon an even date herewith, the disclosure of which is incorporated hereinby reference.

An embodiment of this invention relates to a process for producing oneor more substituted or unsubstituted 6-hydroxyhexanals which comprises:

(a) subjecting one or more substituted or unsubstituted alkadienes,e.g., butadiene, to reductive hydroformylation in the presence of areductive hydroformylation catalyst, e.g., a metal-organophosphorusligand complex catalyst, to produce one or more substituted orunsubstituted unsaturated alcohols comprising 3-penten-1-ols,4-penten-1-ol and/or 2-penten-1-ols;

(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols from the reductive hydroformylation catalyst; and

(c) subjecting said one or more substituted or unsubstituted unsaturatedalcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-olsto hydroformylation in the presence of a hydroformylation catalyst,e.g., a metal-organophosphorus ligand complex catalyst, to produce oneor more substituted or unsubstituted 6-hydroxyhexanals. The reactionconditions in steps (a) and (c) may be the same or different, and thereductive hydroformylation catalyst in step (a) and the hydroformylationcatalyst in step (c) may be the same or different.

Yet another embodiment of this invention relates to a process forproducing one or more substituted or unsubstituted 6-hydroxyhexanalswhich comprises:

(a) subjecting one or more substituted or unsubstituted alkadienes,e.g., butadiene, to reductive hydroformylation in the presence of areductive hydroformylation catalyst, e.g., a metal-organophosphorusligand complex catalyst, to produce one or more substituted orunsubstituted unsaturated alcohols comprising 3-penten-1-ols,4-penten-1-ol and/or 2-penten-1-ols;

(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols from the reductive hydroformylation catalyst;

(c) optionally subjecting the 2-penten-1-ols and/or 3-penten-1-ols toisomerization in the presence of a heterogeneous or homogeneous olefinisomerization catalyst to partially or completely isomerize the2-penten-1-ols and/or 3-penten-1-ols to 3-penten-1-ols and/or4-penten-1-ol; and

(d) subjecting said one or more substituted or unsubstituted unsaturatedalcohols comprising 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-olto hydroformylation in the presence of a hydroformylation catalyst,e.g., a metal-organophosphorus ligand complex catalyst, to produce oneor more substituted or unsubstituted 6-hydroxyhexanals. The reactionconditions in steps (a) and (d) may be the same or different, and thereductive hydroformylation catalyst in step (a) and the hydroformylationcatalyst in step (d) may be the same or different.

The olefin isomerization catalyst in step (c) may be any of a variety ofhomogeneous or heterogeneous transition metal-based catalysts(particularly Ni, Rh, Pd, Pt, Co, Ru, or Ir), or may be a heterogeneousor homogeneous acid catalyst (particularly any acidic zeolite, polymericresin, or source of H+, any of which may be modified with one or moretransition metals). Such olefin isomerization catalysts are known in theart and the isomerization can be conducted by conventional proceduresknown in the art. As used herein, the term "isomerization" iscontemplated to include, but are not limited to, all permissibleisomerization processes which involve converting one or more substitutedor unsubstituted 2-penten-1-ols and/or 3-penten-1-ols to one or moresubstituted or unsubstituted 4-penten-1-ols.

When the processes of this invention are conducted in two stages (i.e.,first producing 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-olunder one set of conditions and then producing a 6-hydroxyhexanal fromthe 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-ol under anotherset of conditions), it is preferred to conduct the first stage at atemperature from 75° C. to 110° C. and at a total pressure from 250 psito 1000 psi and to conduct the second stage at a temperature from 60° C.to 120° C. and at a pressure from 5 psi to 500 psi. The same ordifferent catalysts can be used in the first and second stages. Theother conditions can be the same or different in both stages.

The processes of this invention can be operated over a wide range ofreaction rates (m/L/h=moles of product/liter of reaction solution/hour).Typically, the reaction rates are at least 0.01 m/L/h or higher,preferably at least 0.1 m/L/h or higher, and more preferably at least0.5 m/L/h or higher. Higher reaction rates are generally preferred froman economic standpoint, e.g., smaller reactor size, etc.

The substituted and unsubstituted hydroxyaldehyde products (e.g.,6-hydroxyhexanals) have a wide range of utilities that are well known inthe art, e.g., they are useful as intermediates in the production ofepsilon caprolactone, epsilon caprolactam, adipic acid and1,6-hexanediol.

The processes of this invention may be carried out using, for example, afixed bed reactor, a fluid bed reactor, a continuous stirred tankreactor (CSTR) or a slurry reactor. The optimum size and shape of thecatalysts will depend on the type of reactor used. In general, for fluidbed reactors, a small, spherical catalyst particle is preferred for easyfluidization. With fixed bed reactors, larger catalyst particles arepreferred so the back pressure within the reactor is kept reasonablylow.

The processes of this invention can be conducted in a batch orcontinuous fashion, with recycle of unconsumed starting materials ifrequired. The reaction can be conducted in a single reaction zone or ina plurality of reaction zones, in series or in parallel or it may beconducted batchwise or continuously in an elongated tubular zone orseries of such zones. The materials of construction employed should beinert to the starting materials during the reaction and the fabricationof the equipment should be able to withstand the reaction temperaturesand pressures. Means to introduce and/or adjust the quantity of startingmaterials or ingredients introduced batchwise or continuously into thereaction zone during the course of the reaction can be convenientlyutilized in the processes especially to maintain the desired molar ratioof the starting materials. The reaction steps may be effected by theincremental addition of one of the starting materials to the other.Also, the reaction steps can be combined by the joint addition of thestarting materials. When complete conversion is not desired or notobtainable, the starting materials can be separated from the product,for example by distillation, and the starting materials then recycledback into the reaction zone.

The processes may be conducted in either glass lined, stainless steel orsimilar type reaction equipment. The reaction zone may be fitted withone or more internal and/or external heat exchanger(s) in order tocontrol undue temperature fluctuations, or to prevent any possible"runaway" reaction temperatures.

The processes of this invention may be conducted in one or more steps orstages. The exact number of reaction steps or stages will be governed bythe best compromise between achieving high catalyst selectivity,activity, lifetime and ease of operability, as well as the intrinsicreactivity of the starting materials in question and the stability ofthe starting materials and the desired reaction product to the reactionconditions.

In an embodiment, the processes useful in this invention may be carriedout in a multistaged reactor such as described, for example, incopending U.S. patent application Ser. No.08/757,743, filed on Nov. 26,1996, the disclosure of which is incorporated herein by reference. Suchmultistaged reactors can be designed with internal, physical barriersthat create more than one theoretical reactive stage per vessel. Ineffect, it is like having a number of reactors inside a singlecontinuous stirred tank reactor vessel. Multiple reactive stages withina single vessel is a cost effective way of using the reactor vesselvolume. It significantly reduces the number of vessels that otherwisewould be required to achieve the same results. Fewer vessels reduces theoverall capital required and maintenance concerns with separate vesselsand agitators.

The substituted and unsubstituted hydroxyaldehydes, e.g.,6-hydroxyhexanals, produced by the processes of this invention canundergo further reaction(s) to afford desired derivatives thereof. Suchpermissible derivatization reactions can be carried out in accordancewith conventional procedures known in the art. Illustrativederivatization reactions include, for example, hydrogenation,esterification, etherification, amination, alkylation, dehydrogenation,reduction, acylation, condensation, carboxylation, carbonylation,oxidation, cyclization, silylation and the like, including permissiblecombinations thereof. Preferred derivatization reactions and derivativesof 6-hydroxyhexanal include, for example, reductive amination to givehexamethylenediamine, oxidation to give adipic acid, oxidation andcyclization to give epsilon caprolactone, oxidation, cyclization andamination to give epsilon caprolactam, and hydrogenation or reduction togive 1,6-hexanediols. This invention is not intended to be limited inany manner by the permissible derivatization reactions or permissiblederivatives of substituted and unsubstituted 6-hydroxyhexanals.

For purposes of this invention, the term "hydrocarbon" is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. Such permissible compounds may also have one or moreheteroatoms. In a broad aspect, the permissible hydrocarbons includeacyclic (with or without heteroatoms) and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticorganic compounds which can be substituted or unsubstituted.

As used herein, the term "substituted" is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements reproduced in "BasicInorganic Chemistry" by F. Albert Cotton, Geoffrey Wilkinson and Paul L.Gaus, published by John Wiley and Sons, Inc., 3rd Edition, 1995.

Certain of the following examples are provided to further illustratethis invention.

EXAMPLE 1

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.31 grams of Ligand Fidentified above (5:1 ligand to rhodium ratio), and 25 milliliters oftetrahydrofuran was charged to a 100 milliliter Parr reactor. Butadiene(1.5 milliliters) was charged to the reactor as a liquid under pressure.The reaction was heated to 95° C. and pressurized to 250 psig with 4:1carbon monoxide:hydrogen. After one hour the solution was analyzed bygas chromatography to determine product composition. Butadiene was 37%by weight converted. The products consisted of 75% by weight3-pentenals, 2% by weight 2-pentenals, 6% by weight 4-pentenal, 2% byweight valeraldehyde, and 5% by weight adipaldehyde.

EXAMPLE 2

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.31 grams of Ligand Fidentified above (5:1 ligand to rhodium ratio), and 25 milliliters ofdiglyme was charged to a 100 milliliter Parr reactor. Butadiene (7milliliters) was charged to the reactor as a liquid under pressure. Thereaction was heated to 95° C. and pressurized to 1000 psig with 4:1carbon monoxide:hydrogen. The solution was analyzed by gaschromatography at intervals to determine product composition. Theresults are shown in Table A below.

                                      TABLE A                                     __________________________________________________________________________    Reaction                     Branched                                         Time 3-Pentenals                                                                         4-Pentenal                                                                         2-Pentenals                                                                         Valeraldehyde                                                                        Dialdehyde                                                                          Adipaldehyde                               (Minutes)                                                                          (Wt. %)                                                                             (Wt. %)                                                                            (Wt. %)                                                                             (Wt. %)                                                                              (Wt. %)                                                                             (Wt. %)                                    __________________________________________________________________________    10   75    11   1            2      8                                         30   74    8    3     1      3     10                                         60   68    3    5     2      5     15                                         90   55         7     9      8     19                                         120  36         6     24     11    22                                         __________________________________________________________________________

EXAMPLE 3

A catalyst solution consisting of 0.136 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 3 grams of Ligand Fidentified above (3.6:1 ligand to rhodium ratio), and 150 milliliters oftetrahydrofuran was charged to a 300 milliliter Parr autoclave.Butadiene (100 milliliters) was charged as a liquid under pressure. Thereaction was heated to 95° C. and pressurized to 800 psi with 4:1 carbonmonoxide:hydrogen. The reaction was periodically repressurized to 900psi with syngas (1:1 carbon monoxide:hydrogen) to compensate for thatabsorbed by the solution. After 4 hours, the mixture was analyzed by gaschromatography to determine the product composition. The productsconsisted of 80% by weight pentenals, 11% by weight valeraldehyde, and4% by weight adipaldehyde.

EXAMPLE 4

A catalyst solution consisting of 0.012 grams of rhodium dicarbonylacetylacetonate (200 parts per million rhodium), 0.47 grams of Ligand Eidentified above (12:1 ligand to rhodium ratio), and 15 milliliters oftetrahydrofuran was charged to a 100 milliliter Parr reactor. Butadiene(2 milliliters) was charged to the reactor as a liquid under pressure.The reaction was heated to 95° C. and pressurized to 500 psig with 1:1carbon monoxide:hydrogen. The reaction rate was determined by monitoringthe rate of syngas (1:1 carbon monoxide:hydrogen) consumption. The rateof reaction was found to be 0.4 mol/l-hr. After two hours of reactionthe solution was analyzed by gas chromatography to determine productcomposition. Butadiene was 95% by weight converted. The productsconsisted of 75% by weight 3-pentenals, 3% by weight 4-pentenal, 5% byweight 2-pentenals, 7% by weight valeraldehyde, 1% by weight brancheddialdehyde, and 9% by weight adipaldehyde.

EXAMPLE 5

A catalyst solution consisting of 0.012 grams of rhodium dicarbonylacetylacetonate (200 parts per million rhodium), 0.47 grams of Ligand Didentified above (14:1 ligand to rhodium ratio), and 15 milliliters oftetrahydrofuran was charged to a 100 milliliter Parr reactor. Butadiene(2 milliliters) was charged to the reactor as a liquid under pressure.The reaction was heated to 95° C. and pressurized to 500 psig with 1:1carbon monoxide:hydrogen. The reaction rate was determined by monitoringthe rate of syngas (1:1 carbon monoxide:hydrogen) consumption. The rateof reaction was found to be 1.2 mol/l-hr. After two hours of reactionthe solution was analyzed by gas chromatography to determine productcomposition. Butadiene was 68% by weight converted. The productsconsisted of 70% by weight 3-pentenals, 8% by weight 4-pentenal, 8% byweight 2-pentenals, 8% by weight valeraldehyde, 1% by weight brancheddialdehyde, and 5% by weight adipaldehyde.

EXAMPLE 6

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.42 grams of theligand depicted below (6:1 ligand to rhodium ratio), 2.29 grams ofN-methypyrrolidinone (as an internal standard) and 25 milliliters oftetrahydrofuran was charged to a 100 milliliter Parr reactor. Butadiene(3 milliliters) was charged to the reactor as a liquid under pressure.The reaction was heated to 95° C. and pressurized to 500 psig with 1:1carbon monoxide:hydrogen. After two hours of reaction the solution wasanalyzed by gas chromatography to determine product composition.Butadiene was 33% by weight converted. The products consisted of 87% byweight 3-pentenals, 3% by weight 2-pentenals, 4% by weight 4-pentenal,and 7% by weight valeraldehyde. ##STR32##

EXAMPLE 7

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.88 grams of theligand depicted below (10-15:1 ligand to rhodium ratio), 2.19 grams ofN-methylpyrrolidinone (as an internal standard) and 25 milliliters oftetrahydrofuran was charged to a 100 milliliter Parr reactor. Butadiene(3 milliliters) was charged to the reactor as a liquid under pressure.The reaction was heated to 95° C. and pressurized to 500 psig with 1:1carbon monoxide:hydrogen. After two hours of reaction the solution wasanalyzed by gas chromatography to determine product composition.Butadiene was 33% by weight converted. The products consisted of 80% byweight 3-pentenals, 8% by weight 4-pentenal, 4% by weight 2-pentenals,and 8% by weight valeraldehyde. ##STR33##

EXAMPLE 8

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.09 grams of theligand depicted below (1.5:1 ligand to rhodium ratio), and 25milliliters of tetrahydrofuran was charged to a 100 milliliter Parrreactor. Butadiene (1 milliliter) was charged to the reactor as a liquidunder pressure. The reaction was heated to 95° C. and pressurized to 500psig with 4:1 carbon monoxide:hydrogen. After one hour the solution wasanalyzed by gas chromatography to determine product composition.Butadiene w as 51% by weight converted. The products consisted of 79% byweight 3-pentenals, 12% by weight 4-pentenal, and 5% by weight butenes.##STR34##

EXAMPLE 9

A catalyst solution consisting of 0.016 grams of rhodium dicarbonylacetylacetonate and 2.089 grams of Ligand F identified above (3.6:1ligand to rhodium ratio) and 160 milliliters of tetraglyme was chargedto a 300 milliliter Parr autoclave. Butadiene (35 milliliters) wascharged as a liquid under pressure. The reaction was heated to 95° C.and pressurized to 900 psi with 4:1 carbon monoxide:hydrogen. Thereaction was periodically repressurized to 900 psi with syngas (1:1carbon monoxide:hydrogen) to compensate for that absorbed by thesolution. After 2.5 hours, the reactor was cooled and recharged with 35milliliters of butadiene and the reaction repeated. A total of three 35milliliter butadiene charges were reacted, in order to provide enoughmaterial for distillation. The mixture was analyzed by gaschromatography to determine the product composition. Thehydroformylation products consisted of 53% by weight pentenals, 27% byweight valeraldehyde, and 12% by weight adipaldehyde. The productmixture was distilled at 260 mm Hg through a 25-tray Oldershaw column.The best distillation cuts, collected a t a kettle temperature of 225°C., consisted of 77% by weight pentenals.

EXAMPLE 10

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.18 grams oftriphenylphosphine ligand (10:1 ligand to rhodium ratio), and 25milliliters of tetrahydrofuran was charged to a 100 milliliter Parrreactor. Butadiene (1 milliliter) was charged to the reactor as a liquidunder pressure. The reaction was heated to 95° C. and pressurized to 500psig with 1:1 carbon monoxide:hydrogen. After one h our the solution wasanalyzed by gas chromatography to determine product composition.Butadiene was approximately 60% by weight converted. The productsconsisted of 82% by weight 3-pentenals, 9% by weight 4-pentenal, 5% byweight valeraldehyde, and 4% by weight butenes. After two hours reactiontime, the products consisted of 69% by weight 3-pentenals, 3% by weight4-pentenal, 12% by weight valeraldehyde, 5% by weight adipaldehyde, 4%by weight methylglutaraldehyde, 3% by weight butenes, and 2% by weight2-methylbutyraldehyde.

EXAMPLE 11

A catalyst solution consisting of 0.032 grams of rhodium dicarbonylacetylacetonate (500 parts per million rhodium), 0.12 grams oftris(2-cyanoethyl)phosphine ligand (5:1 ligand to rhodium ratio), and 25milliliters of tetrahydrofuran was charged to a 100 milliliter Parrreactor. Butadiene (3 milliliters) was charged to the reactor as aliquid under pressure. The reaction was heated to 110° C. andpressurized to 1000 psig with 1:1 carbon monoxide:hydrogen. After twohours of reaction the solution was analyzed by gas chromatography todetermine product composition. Butadiene was approximately 68% by weightconverted. The products consisted of 54% by weight 3-pentenals, 5% byweight 4-pentenal, 3% by weight 2-pentenals, 27% by weightvaleraldehyde, and 7% by weight 2-methylbutyraldehyde.

EXAMPLE 12

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.20 grams ofdiphenyl(o-methoxyphenyl)phosphine ligand (10:1 ligand to rhodiumratio), and 25 milliliters of tetrahydrofuran was charged to a 100milliliter Parr reactor. Butadiene (3 milliliters) was charged to thereactor as a liquid under pressure. The reaction was heated to 95° C.and pressurized to 500 psig with 1:1 carbon monoxide:hydrogen. After onehour the solution was analyzed by gas chromatography to determineproduct composition. Butadiene was approximately 50% by weightconverted. The products consisted of 74% by weight 3-pentenals, 10% byweight 4-pentenal, 6% by weight valeraldehyde, and 8% by weight butenes.

EXAMPLE 13

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.24 grams ofbis(diphenylphosphino)propane ligand (8:1 ligand to rhodium ratio), and25 milliliters of tetrahydrofuran was charged to a 100 milliliter Parrreactor. Butadiene (3 milliliters) was charged to the reactor as aliquid under pressure. The reaction was heated to 95° C. and pressurizedto 500 psig with 1:1 carbon monoxide:hydrogen. After two hours ofreaction the solution was analyzed by gas chromatography to determineproduct composition. Butadiene was 50% by weight converted. The productsconsisted of only C5 aldehydes, with no dialdehyde present.

EXAMPLE 14

A catalyst solution consisting of 0.018 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.16 grams ofisopropyldiphenylphosphine ligand (5:1 ligand to rhodium ratio), and 25milliliters of tetrahydrofuran was charged to a 100 milliliter Parrreactor. Butadiene (1 milliliter) was charged to the reactor as a liquidunder pressure. The reaction was heated to 95° C. and pressurized to 500psig with 1:1 carbon monoxide:hydrogen. After two hours of reaction thesolution was analyzed by gas chromatography to determine productcomposition. Butadiene was approximately 46% by weight converted. Theproducts consisted of 79% by weight 3-pentenals, 9% by weight4-pentenal, 5% by weight valeraldehyde, and 5% by weight butenes.

EXAMPLE 15

A catalyst solution consisting of 0.018 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.08 grams ofbis(diphenylphosphino)ferrocene ligand (2:1 ligand to rhodium ratio),and 25 milliliters of tetrahydrofuran was charged to a 100 milliliterParr reactor. Butadiene (1 milliliter) was charged to the reactor as aliquid under pressure. The reaction was heated to 75° C. and pressurizedto 1000 psig with 10:1 carbon monoxide:hydrogen. After two hours ofreaction the solution was analyzed by gas chromatography to determineproduct composition. Butadiene was approximately 54% by weightconverted. The products consisted of 74% by weight 3-pentenals, and 25%by weight 4-pentenal.

EXAMPLE 16

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.31 grams of Ligand F(5:1 ligand to rhodium ratio), 10 microliters of trimethylphosphineligand (2:1 ligand to rhodium ratio), and 25 milliliters of toluene wascharged to a 100 milliliter Parr reactor. Butadiene (3 milliliters) wascharged to the reactor as a liquid under pressure. The reaction washeated to 110° C. and pressurized to 1000 psig with 1:1 carbonmonoxide:hydrogen. After two hours the solution was analyzed by gaschromatography to determine product composition. Butadiene was 80% byweight converted. The products consisted of 53% by weight 3-pentenals,13% by weight 2-pentenals, 4% by weight 4-pentenal, 8% by weightvaleraldehyde, 8% by weight adipaldehyde, and 7% by weight butenes.

EXAMPLE 17

A catalyst solution consisting of 0.019 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.12 grams of Ligand Fidentified above (2:1 ligand to rhodium ratio), 0.09 grams oftris(p-tolyl)phosphine ligand (4:1 ligand to rhodium ratio), and 25milliliters of tetrahydrofuran was charged to a 100 milliliter Parrreactor. Butadiene (3 milliliters) was charged to the reactor as aliquid under pressure. The reaction was heated to 95° C. and pressurizedto 500 psig with 1:1 carbon monoxide:hydrogen. After two hours thesolution was analyzed by gas chromatography to determine productcomposition. Butadiene was 80% by weight converted. The productsconsisted of 51% by weight 3-pentenals, 5% by weight 2-pentenals, 26% byweight valeraldehyde, and 15% by weight adipaldehyde.

EXAMPLE 18

A catalyst solution consisting of 0.05 grams of (bicyclo2.2.1!hepta-2,5-diene)1,1'-bis(diphenylphosphino)ferrocene!rhodium(I)perchlorate (250 partsper million rhodium) in 25 milliliters of tetrahydrofuran was charged toa 100 milliliter Parr reactor. Butadiene (3 milliliters) was charged tothe reactor as a liquid under pressure. The reaction was heated to 95°C. and pressurized to 400 psig with 1:1 carbon monoxide:hydrogen. Afterone hour of reaction the solution was analyzed by gas chromatography todetermine product composition. Butadiene was approximately 50% by weightconverted. The products consisted of 28% by weight 3-pentenals, 36% byweight 4-pentenal, 7% by weight 2-pentenals, 8% by weight valeraldehyde,and 21% by weight low molecular weight products, possibly butenes.

EXAMPLE 19

A catalyst solution consisting of 0.05 grams of (bicyclo2.2.1!hepta-2,5-diene)1,1'-bis(diphenylphosphino)ferrocene!rhodium(I)perchlorate (250 partsper million rhodium) in 25 milliliters of tetrahydrofuran was charged toa 100 milliliter Parr reactor. Butadiene (3 milliliters) was charged tothe reactor as a liquid under pressure. The reaction was heated to 95°C. and pressurized to 500 psig with 10:1 carbon monoxide:hydrogen. Afterone hour of reaction the solution was analyzed by gas chromatography todetermine product composition. Butadiene was approximately 25% by weightconverted. The products consisted of 17% by weight 3-pentenals, 34% byweight 4-pentenal, and 43% by weight low molecular weight products,possibly butenes.

EXAMPLE 20

A catalyst solution consisting of 0.02 grams of bis(bicyclo2.2.1!hepta-2,5-diene)rhodium(I)perchlorate/bis(diphenylphosphino)ferrocene(250 parts per million rhodium) and 0.03 grams ofbis(diphenylphosphino)ferrocene in 25 milliliters of tetrahydrofuran wascharged to a 100 milliliter Parr reactor. Butadiene (3 milliliters) wascharged to the reactor as a liquid under pressure. The reaction washeated to 95° C. and pressurized to 500 psig with 1:1 carbonmonoxide:hydrogen. After 30 minutes of reaction the solution wasanalyzed by gas chromatography to determine product composition.Butadiene conversion was undetermined. The products consisted of 38% byweight 3-pentenals, 43% by weight 4-pentenal, and 20% by weight lowmolecular weight products, possibly butenes.

EXAMPLE 21

A catalyst solution consisting of 0.018 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.035 grams of(4R,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneligand (1:1 ligand to rhodium ratio), and 25 milliliters oftetrahydrofuran was charged to a 100 milliliter Parr reactor. Butadiene(3 milliliters) was charged to the reactor as a liquid under pressure.The reaction was heated to 95° C. and pressurized to 250 psig with 4:1carbon monoxide:hydrogen. After thirty minutes of reaction the solutionwas analyzed by gas chromatography to determine product composition. Theproducts consisted of 57% by weight 3-pentenals, and 32% by weight4-pentenal. After 2 hours of reaction, butadiene was approximately 83%by weight converted. The products consisted of 53% by weight3-pentenals, 8% by weight 4-pentenal, 3% by weight valeraldehyde, 6% byweight branched dialdehydes, and 22% by weight adipaldehyde.

EXAMPLE 22

A catalyst solution consisting of 0.018 grams of rhodium dicarbonylacetylacetonate (300 parts per million rhodium), 0.35 grams of(4R,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneligand (10:1 ligand to rhodium ratio), and 25 milliliters oftetrahydrofuran was charged to a 100 milliliter Parr reactor. Butadiene(3 milliliters) was charged to the reactor as a liquid under pressure.The reaction was heated to 95° C. and pressurized to 500 psig with 1:1carbon monoxide:hydrogen. After 2 hours of reaction, the solution wasanalyzed by gas chromatography to determine product composition.Butadiene was greater than 90% by weight converted. The productsconsisted of 41% by weight 3-pentenals, 3% by weight 2-pentenals, 8% byweight valeraldehyde, 10% by weight branched dialdehydes, and 24% byweight adipaldehyde.

EXAMPLES 23-41

Into a 100 milliliter overhead stirred high pressure reactor was charged0.25 mmol of dicarbonylacetylacetonato rhodium (I), 0.9 mmol of atrialkylphosphine defined in Table B below, 3 milliliters of butadiene,26 milliliters of a solvent as defined in Table B, and 1 milliliter ofdiglyme as internal standard. The reactor was pressurized with 5-10 psiof hydrogen/carbon monoxide in 1/1 ratio and heated to the desiredtemperature set out in Table B. At the desired temperature, the reactorwas pressurized to the desired hydrogen/carbon monoxide ratio set out inTable B and the gas uptake was monitored. After a decrease in pressureof 10%, the reactor was re-pressurized to the initial value withhydrogen/carbon monoxide in 1/1 ratio. Samples of the reaction mixturewere taken in dry ice cooled vials via the sampling line at scheduledintervals and analyzed by gas chromatography. At the end of the reactionperiod of 90 minutes, the gases were vented and the reaction mixturedrained. Further details and results of analyses are set out in Table B.

                                      TABLE B                                     __________________________________________________________________________    Ex.                    Temp.                                                                             H.sub.2 /CO                                                                       Butadiene                                                                          Rate                                                                              SeIectivity (%)                       No.                                                                              Solvent/Promoter                                                                       Phosphine  (°C.)                                                                      (psi)                                                                             Conv. (%)                                                                          m/L/h                                                                             3 & 4 Pentenols                       __________________________________________________________________________    23 Ethanol  Triethylphosphine                                                                        60  300/300                                                                           27   0.2 92                                    24 Ethanol  Triethylphosphine                                                                        80  300/300                                                                           90   1.6 87                                    25 Ethanol  Triethylphosphine                                                                        80  500/500                                                                           87   1.3 91                                    26 Ethanol  Triethylphosphine                                                                        80  75/75                                                                             75   0.3 71                                    27 Octanol  Trioctylphosphine                                                                        80  600/200                                                                           98   1.9 88                                    28 3-Pentenol                                                                             Trioctylphosphine                                                                        80  600/200                                                                           89   nd  90                                    29 Hexanediol                                                                             Trioctylphosphine                                                                        80  300/300                                                                           65   nd  93                                    30 Pyrrole  Trioctylphosphine                                                                        80  600/200                                                                           90   1.4 88                                    31 Ethanol  Tributylphosphine                                                                        80  300/300                                                                           55   1.0 70                                    32 Phenol/THF                                                                             Trioctylphosphine                                                                        80  600/200                                                                           84   2.0 55                                    33 t-Butanol                                                                              Triethylphosphine                                                                        120 250/250                                                                           99   nd  38 (15 min rxn. time)                 34 Ethanol  Trimethylphosphine                                                                       120 250/250                                                                           97   nd  42 (2 h rxn. time)                    35 Ethanol  Diethyl-para-N,N-                                                                        80  600/200                                                                           70   1.2 64                                                dimethylphenylphosphine                                           36 Ethanol/Acetonitrile                                                                   Triethylphosphine                                                                        80  300/300                                                                           68   1.1 82                                    37 Ethanol/Tetraglyme                                                                     Triethylphosphine                                                                        80  300/300                                                                           64   1.0 91                                    38 Diphenylamine                                                                          Trioctylphosphine                                                                        80  600/200                                                                           80   0.8 54                                    39 Acetamide                                                                              Trioctylphosphine                                                                        80  600/200                                                                           85   0.9 34                                    40 Methylacetamide                                                                        Trioctytphosphine                                                                        80  600/200                                                                           73   0.8 59                                    41 N-Methylformamide                                                                      Trioctylphosphine                                                                        80  600/200                                                                           33   0.1 19                                    __________________________________________________________________________     nd = not determined                                                      

EXAMPLES 42-48

Into a 100 milliliter overhead stirred high pressure reactor was charged0.25 mmol of dicarbonylacetylacetonato rhodium (I), 0.9 mmol of atrialkylphosphine defined in Table C below, 3 milliliters of butadiene,26 milliliters of ethanol, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 5-10 psi of hydrogen/carbonmonoxide in 1/1 ratio and heated to 80° C. At the desired temperature,the reactor was pressurized to the desired hydrogen/carbon monoxideratio set out in Table C and the gas uptake was monitored. After adecrease in pressure of 10%, the reactor was re-pressurized to theinitial value with hydrogen/carbon monoxide in 1/1 ratio. Samples of thereaction mixture were taken in dry ice cooled vials via the samplingline at scheduled intervals and analyzed by gas chromatography. At theend of the reaction period of 120 minutes, the gases were vented and thereaction mixture drained. Further details and results of analyses areset out in Table C.

                  TABLE C                                                         ______________________________________                                                                        Rate                                          Ex.              H.sub.2 CO                                                                            Butadiene                                                                            (m/L/                                                                              Selectivity (%)                          No.  Phosphine   (psi)   Conv   h)   3 & 4 Pentenols                          ______________________________________                                        42   t-butyldiethyl                                                                            300/300 60     0.8  13                                            phosphine                                                                43   t-butyldiethyl                                                                            800/200 69     1.1  19                                            phosphine                                                                44   cyclohexyldiethyl                                                                         300/300 76     0.7  75                                            phosphine                                                                45   cyclohexyldiethyl                                                                         800/200 82     1.4  80                                            phosphine                                                                46   n-butyldiethyl                                                                            300/300 77     1.1  82                                            phosphine                                                                47   diethylphenyl                                                                             200/800 53     0.9  77                                            phosphine                                                                48   ethyldiphenyl                                                                             200/800 38     0.6  27                                            phosphine                                                                ______________________________________                                    

EXAMPLE 49

A 160 milliliter magnetically stirred autoclave was purged with 1:1 H₂/CO and charged with a catalyst solution consisting of 0.1125 grams(0.44 mmol) dicarbonylacetylacetonato rhodium (I), 0.3515 grams (2.94mmol) P(CH₂ CH₂ CH₂ OH)₃, and 44.1 grams tetrahydrofuran. The autoclavewas pressurized with 40 psig 1:1 H₂ /CO and heated to 80° C. 6milliliters (3.73 grams) of 1,3-butadiene was charged with a meteringpump and the reactor was pressurized to 1000 psig with 1:1 H₂ /CO. Thereaction mixture was maintained at 80° C. under 1000 psi 1:1 H₂ /CO.Samples of the reaction mixture taken after 90 minutes and 170 minutesprovided the results set out in Table D below.

                  TABLE D                                                         ______________________________________                                               Temper-          Butadiene                                             Time   ature    H.sub.2 /CO                                                                           Conver-                                                                              Rate  Selectivity (%)                          (minutes)                                                                            (°C.)                                                                           (psig)  sion (%)                                                                             (m/L/h)                                                                             3 & 4 Pentenols                          ______________________________________                                         90    80       500/500 81     0.7   66                                       170    80       500/500 96     0.4   72                                       ______________________________________                                    

EXAMPLE 50

A 160 milliliter magnetically stirred autoclave was purged with 1:1 H₂/CO and charged with a catalyst solution consisting of 0.1126 grams(0.44 mmol) dicarbonylacetylacetonato rhodium (I), 0.6120 grams (1.69mmol) P(CH₂ CH₂ CH₂ OH)₃, and 39.9 grams of ethanol. The autoclave waspressurized with 40 psig 1:1 H₂ /CO and heated to 80° C. 6 milliliters(3.73 grams) of 1,3-butadiene was charged with a metering pump and thereactor pressurized to 1000 psig with 1:1 H₂ /CO. The reaction mixturewas maintained at 80° C. under 1000 psi 1:1 H₂ /CO. Samples of thereaction mixture taken after 15 and 43 minutes provided the results setout in Table E below.

                  TABLE E                                                         ______________________________________                                               Temper-          Butadiene                                             Time   ature    H.sub.2 /CO                                                                           Conver-                                                                              Rate  Selectivity (%)                          (minutes)                                                                            (°C.)                                                                           (psig)  sion (%)                                                                             (m/L/h)                                                                             3 & 4 Pentenols                          ______________________________________                                        15     80       500/500 53     2.6   70                                       43     80       500/500 89     1.5   78                                       ______________________________________                                    

EXAMPLE 51

A 100 milliliter overhead stirred high pressure reactor was charged with0.12 mmol rhodium(I) dicarbonyl acetylacetonate, 2.2 mmoltriphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters ofethyl alcohol, and 1 milliliter of diglyme as internal standard. Thereactor was pressurized with 5 psi carbon monoxide and hydrogen in a 1:1ratio, heated to 105° C., and then pressurized to 30 psi carbon monoxideand hydrogen. A sample of the reaction mixture was after 0.5 hours, andthen analyzed by gas chromatography. Details of the reaction are set outin Table F below.

EXAMPLE 52

A 100 milliliter overhead stirred high pressure reactor was charged with0.25 mmol rhodium(I) dicarbonyl acetylacetonate, 4.9 mmoltriphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters oftetrahydrofuran, and 1 milliliter of diglyme as internal standard. Thereactor was pressurized with 10 psi carbon monoxide and hydrogen in a1:1 ratio, heated to 75° C., and then pressurized to 50 psi carbonmonoxide and hydrogen. Samples of the reaction mixture were taken attime zero and after 5.5 hours, and then analyzed by gas chromatography.At the end of the reaction (5.5 hours), the gases were vented and thereaction mixture drained. Details of the reaction are set out in TableF.

EXAMPLE 53

A 100 milliliter overhead stirred high pressure reactor was charged with0.22 mmol rhodium(I) dicarbonyl acetylacetonate, 4.4 mmoltriphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters ofethyl alcohol, and 1 milliliter of diglyme as internal standard. Thereactor was pressurized with 10 psi carbon monoxide and hydrogen in a1:1 ratio, heated to 75° C., and then pressurized to 50 psi carbonmonoxide and hydrogen. Samples of the reaction mixture were taken attime zero and after 20 hours, and then analyzed by gas chromatography.At the end of the reaction (20 hours), the gases were vented and thereaction mixture drained. Details of the reaction are set out in TableF.

EXAMPLE 54

A 100 milliliter overhead stirred high pressure reactor was charged with0.25 mmol rhodium(I) dicarbonyl acetylacetonate, 4.9 mmoltriphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters oftetrahydrofuran, and 1 milliliter of diglyme as internal standard. Thereactor was pressurized with 5 psi carbon monoxide and hydrogen in a 1:1ratio, heated to 100° C., and then pressurized to 30 psi carbon monoxideand hydrogen. Samples of the reaction mixture were taken at time zeroand after 1.5 hours, and then analyzed by gas chromatography. At the endof the reaction (1.5 hours), the gases were vented and the reactionmixture drained. Details of the reaction are set out in Table F.

EXAMPLE 55

A 100 milliliter overhead stirred high pressure reactor was charged with0.27 mmol rhodium(I) dicarbonyl acetylacetonate, 0.29 mmol(R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 1.5 milliliters ofcis-3-pentenol, 26 milliliters of tetrahydrofuran, and 1 milliliter ofdiglyme as internal standard. The reactor was pressurized with 10 psicarbon monoxide and hydrogen in a 1:1 ratio, heated to 75° C., and thenpressurized to 120 psi carbon monoxide and hydrogen. Samples of thereaction mixture were taken at time zero and after 2 hours, and thenanalyzed by gas chromatography. At the end of the reaction (2 hours),the gases were vented and the reaction mixture drained. Details of thereaction are set out in Table F.

                                      TABLE F                                     __________________________________________________________________________                          Pent.                                                   Ex.           Temp.                                                                             CO/H.sub.2                                                                        Con.                                                                             Rate                                                                              C5.sup.a                                                                         C5.sup.b                                                                         Et5L                                                                             Me6L                                                                              6-HH                                No.                                                                              Metal                                                                            Ligand                                                                            Solvent                                                                           (°C.)                                                                      (psi)                                                                             (%)                                                                              (M/l-h)                                                                           (%)                                                                              (%)                                                                              (%)                                                                              (%) (%)                                 __________________________________________________________________________    51 Rh TPP EtOH                                                                              105 15115                                                                             18 n.d.                                                                              14 37  7 15  25                                  52 Rh TPP THF 75  25/25                                                                             63 0.06                                                                               1  7 34 47  10                                  53 Rh TPP EtOH                                                                              75  25/25                                                                             40 0.01                                                                               2 12 36 34  14                                  54 Rh TPP THP 100 15/15                                                                             40 0.15                                                                              13 47  3 11  15                                  55 Rh BINAP                                                                             THF 75  60/60                                                                             35 0.10                                                                               6 83  0  9   1                                  __________________________________________________________________________     Pent. Conv = cis3-pentenol conversion; C5.sup.a = 1pentanol +                 valeraldehyde + 2pentenol; C5.sup.6 = trans3-pentenol + 4pentenol; Et5L =     2ethylbutyrolactol; Me6L = 2methylvalerolactol; 6HH = 6hydroxyhexanal; TP     = triphenylphosphine; BINAP =                                                 (R)(+)2,2bis(diphenylphosphine)-1,1binaphthyl; EtOH = ethyl alcohol; THR      tetrahydrofuran.                                                         

EXAMPLE 56

A 100 milliliter overhead stirred high pressure reactor was charged with0.10 mmol of dicarbonylacetylacetonato rhodium (I), about 0.20 mmol of2,2'-(bisdiphenylphosphinomethyl)1,1'-biphenyl, 1 milliliter of4-pentenol, 26 milliliters of ethanol, and 1 milliliter of diglyme asinternal standard. The reactor was pressurized with 5-10 psi of 1/1hydrogen/carbon monoxide, and heated to 90° C. At 90° C., the reactorwas pressurized to 250 psi with 1/1 hydrogen/carbon monoxide at stirredfor 1 hour. The reactor gases were vented and the reaction mixturedrained and analyzed by gas chromatography. 6-Hydroxyhexanal was formedin 97% selectivity.

EXAMPLES 57-60

Into a 100 milliliter overhead stirred high pressure reactor was charged0.07 mmol of dicarbonylacetylacetonato rhodium (I), 0.35 mmol of abisphosphite ligand as identified in Table G below and depicted in theabove specification, 25 milliliters of tetrahydrofuran, and 0.5milliliter of diglyme as internal standard. The reactor was pressurizedwith 50 psi of hydrogen/carbon monoxide in 1/1 ratio and heated to thetemperature in Table G. At the desired temperature, 1.0 milliliter of3-pentenol was added and the reactor was pressurized to the desiredhydrogen/carbon monoxide pressures set out in Table G. After a 5% dropin the reactor pressure, the reactor was re-pressurized to the initialvalue with hydrogen/carbon monoxide in 1/1 ratio. At the end of thereaction period of 120 minutes, the gases were vented and the reactionmixture drained and analyzed by gas chromatography. Further details andresults of analyses are set out in Table G.

                  TABLE G                                                         ______________________________________                                                                     3-     Selectivity to                            Ex.  Bisphosphite                                                                            Temp.   H.sub.2 /CO                                                                         Pentenol                                                                             6-hydroxyhexanal                          No.  ligand    (°C.)                                                                          (psi) Conv. (%)                                                                            (%)                                       ______________________________________                                        57   Ligand F  85      100/100                                                                             68     60                                        58   Ligand F  95      200/50                                                                              94     59                                        59   Ligand D  85      100/100                                                                             44     65                                        60   Ligand D  95      333/167                                                                             52     58                                        ______________________________________                                    

EXAMPLES 61-65

Into a 100 milliliter overhead stirred high pressure reactor was charged0.07 mmol of dicarbonylacetylacetonato rhodium (I), 0.35 mmol of abisphosphite ligand as identified in Table H below depicted below or inthe above specification, 25 milliliters of tetrahydrofuran, and 0.5milliliter of digylme as internal standard. The reactor was pressurizedwith 50 psi of hydrogen/carbon monoxide 1 ratio and heated to 95° C. Atthe desired temperature, 1.0 liter of 3-pentenol was added and thereactor was pressurized to psi with hydrogen/carbon monoxide in 1/1ratio. After a 5% drop in the reactor pressure, the reactor wasre-pressurized to the initial value hydrogen/carbon monoxide in 1/1ratio. At the end of the reaction d of 120 minutes, the gases werevented and the reaction mixture ed and analyzed by gas chromatography.Further details and results of analyses are set out in the Table H.

                  TABLE H                                                         ______________________________________                                                                       Selectivity to 6-                              Ex.                   3-Pentenol                                                                             hydroxyhexanal                                 No.  Bisphosphite ligand                                                                            Conv. (%)                                                                              (%)                                            ______________________________________                                        61   Ligand W         20       59                                             62   Ligand X         50       59                                             63   Ligand E         67       55                                             64   Ligand Y         92       44                                             65   ethylidene bis(di-t-butyl)                                                                     54       29                                                  phenyl (phenylene glycol-P)2                                             ______________________________________                                         ##STR35##                                                                     ##STR36##                                                                     ##STR37##                                                                     ##STR38##                                                                

A 100 milliliter magnetically stirred autoclave was purged N₂ for 30minutes and charged with a solution consisting of 3 milliliters of3-pentenol, 26 milliliters of tetrahydrofuran, Ligand Z identified belowand dicarbonylacetylacetonato Rh (I) in amounts listed in Table I below.The autoclave was pressurized with 60-80% of the total amount of 1:1hydrogen/carbon monoxide and heated to the temperature listed in TableI. The total amount of 1:1 hydrogen/carbon monoxide was as follows: Ex.67-100 psi hydrogen and 100 psi carbon monoxide; Ex. 68-100 psi hydrogenand 100 psi carbon monoxide; Ex. 69-50 psi hydrogen and 50 psi carbonmonoxide; and Ex. 70-100 psi hydrogen and 100 psi carbon monoxide. Afterthe appropriate temperature was reached, the autoclave was pressurizedto the total amount of 1:1 hydrogen/carbon monoxide described above. Thereaction mixture was maintained isothermally under 1:1 hydrogen/carbonmonoxide. Samples of the reaction mixture taken after 150 minutes gavethe results listed in Table I. Selectivities were determined by gaschromatography and referenced to standard response factors. 0.94 grams(7.02 mmol) of diglyme was used as an internal gas chromatographystandard in the reaction mixture.

                  TABLE I                                                         ______________________________________                                                                                 6-Hydroxy-                                        Ligand  Rh(CO).sub.2                                                                         3-pentenol   hexanal                              Ex.  Temp    Z       (acac) Con-   Rate  Selec-                               No.  (°C.)                                                                          (g)     (g)    version                                                                              (m/L/h)                                                                             tivity (%)                           ______________________________________                                        66   85       0.355  0.02   13%    0.5   46.7                                 67   90      1.07    0.07   74%    0.70  54.3                                 68   105     0.14    0.02   96%    0.96  61.2                                 69   95      0.35    0.02   38%    0.41  54.4                                 ______________________________________                                         ##STR39##                                                                

EXAMPLE 70

Tetrarhodium dodecacarbonyl (52.3 milligrams) and Ligand F (1.17 grams)was dissolved in tetraglyme (80 milliliters). To this was added nonane(1.07 grams) as gas chromatograph internal standard, and cis-3-pentenol(25.8 grams). The mixture was charged to a 300 milliliter stirred Parrautoclave and 200 psig of synthesis gas was added (1:1 carbonmonoxide:hydrogen). The reactor temperature was raised to 95° C.,synthesis gas was added to the reactor to bring the pressure to 500psig. The reaction was run for 157 minutes, before being stopped. Gaschromatograph analysis of the reaction mixture showed the followingcomposition: valeraldehyde (23.7%), trans-3-pentenol (8.7%),cis-3-pentenol (13.6%), branched hydroxyaldehyde (5.6%), and6-hydroxyhexanal (52.2%). The identity of the linear and branchedaldehydes was confirmed by gas chromatograph mass spectrometry/infraredspectroscopy.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

We claim:
 1. A process for producing one or more substituted orunsubstituted hydroxyaldehydes which comprises subjecting one or moresubstituted or unsubstituted alkadienes to reductive hydroformylation inthe presence of a reductive hydroformylation catalyst andhydroformylation in the presence of a hydroformylation catalyst toproduce said one or more substituted or unsubstituted hydroxyaldehydes.2. A process for producing one or more substituted or unsubstitutedhydroxyaldehydes which comprises subjecting one or more substituted orunsubstituted pentenals to reductive hydroformylation in the presence ofa reductive hydroformylation catalyst to produce said one or moresubstituted or unsubstituted hydroxyaldehydes.
 3. A process forproducing one or more substituted or unsubstituted hydroxyaldehydeswhich comprises subjecting one or more substituted or unsubstitutedunsaturated alcohols having at least 4 carbon atoms to hydroformylationin the presence of a hydroformylation catalyst to produce said one ormore substituted or unsubstituted hydroxyaldehydes.
 4. A process forproducing one or more substituted or unsubstituted hydroxyaldehydeswhich comprises: (a) subjecting one or more substituted or unsubstitutedalkadienes to reductive hydroformylation in the presence of a reductivehydroformylation catalyst to produce one or more substituted orunsubstituted unsaturated alcohols, and (b) subjecting said one or moresubstituted or unsubstituted unsaturated alcohols to hydroformylation inthe presence of a hydroformylation catalyst to produce said one or moresubstituted or unsubstituted hydroxyaldehydes.
 5. The process of claim 4wherein the substituted or unsubstituted alkadiene comprises butadiene,the substituted or unsubstituted unsaturated alcohols comprisecis-3-penten-1-ol, trans-3-penten-1-ol, 4-penten-1-ol, cis-2-penten-1-oland/or trans-2-penten-1-ol and the substituted or unsubstitutedhydroxyaldehydes comprise 6-hydroxyhexanal.
 6. The process of claim 4wherein the reductive hydroformylation reaction conditions in step (a)and the hydroformylation reaction conditions in step (b) may be the sameor different, and the reductive hydroformylation catalyst in step (a)and the hydroformylation catalyst in step (b) may be the same ordifferent.
 7. The process of claim 6 wherein the reductivehydroformylation catalyst and the hydroformylation catalyst comprise ametal-ligand complex catalyst.
 8. The process of claim 7 wherein saidmetal-ligand complex catalyst comprises a metal selected from a Group 8,9 and 10 metal complexed with an organophosphorus ligand selected from amono-, di-, tri- and poly-(organophosphine) ligand.
 9. The process ofclaim 7 wherein said metal-ligand complex catalyst comprises a metalselected from a Group 8, 9 and 10 metal complexed with anorganophosphorus ligand selected from:(i) a triorganophosphine ligandrepresented by the formula: ##STR40## wherein each R¹ is the same ordifferent and is a substituted or unsubstituted monovalent hydrocarbonradical; (ii) a monoorganophosphite represented by the formula:##STR41## wherein R³ represents a substituted or unsubstituted trivalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater;(iii) a diorganophosphite represented by the formula: ##STR42## whereinR⁴ represents a substituted or unsubstituted divalent hydrocarbonradical containing from 4 to 40 carbon atoms or greater and W representsa substituted or unsubstituted monovalent hydrocarbon radical containingfrom 1 to 18 carbon atoms or greater; (iv) a triorganophosphiterepresented by the formula: ##STR43## wherein each R⁸ is the same ordifferent and is a substituted or unsubstituted monovalent hydrocarbonradical; and (v) an organopolyphosphite containing two or more tertiary(trivalent) phosphorus atoms represented by the formula: ##STR44##wherein X¹ represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁹ is the same or different and is a divalent hydrocarbon radicalcontaining from 4 to 40 carbon atoms, each R¹⁰ is the same or differentand is a substituted or unsubstituted monovalent hydrocarbon radicalcontaining from 1 to 24 carbon atoms, a and b can be the same ordifferent and each have a value of 0 to 6, with the proviso that the sumof a+b is 2 to 6 and n equals a+b.
 10. The process of claim 7 whereinsaid metal-ligand complex catalyst comprises a metal selected from aGroup 8, 9 and 10 metal complexed with an organophosphorus ligand havingthe formula: ##STR45## wherein W represents a substituted orunsubstituted monovalent hydrocarbon radical containing from 1 to 18carbon atoms or greater, each Ar is the same or different and representsa substituted or unsubstituted aryl radical, each y is the same ordifferent and is a value of 0 or 1, Q represents a divalent bridginggroup selected from --C(R⁵)₂ --, --O--, --S--, --NR⁶⁻, Si(R⁷)₂ -- and--CO--, wherein each R⁵ is the same or different and representshydrogen, alkyl radicals having from 1 to 12 carbon atoms, phenyl,tolyl, and anisyl, R⁶ represents hydrogen or a methyl radical, each R⁷is the same or different and represents hydrogen or dial, and m is avalue of 0 or
 1. 11. The process of claim 7 wherein said metal-ligandcomplex catalyst comprises a metal selected from a Group 8, 9 and 10metal complexed with an organophosphorus ligand having the formulaselected from: ##STR46## wherein X¹ represents a substituted orunsubstituted n-valent hydrocarbon bridging radical containing from 2 to40 carbon atoms, each R⁹ is the same or different and is a divalenthydrocarbon radical containing from 4 to 40 carbon atoms, and each R¹⁰is the same or different and is a substituted or unsubstitutedmonovalent hydrocarbon radical containing from 1 to 24 carbon atoms. 12.The process of claim 7 wherein said metal-ligand complex catalystcomprises a metal selected from a Group 8, 9 and 10 metal complexed withan organophosphorus ligand having the formula selected from: ##STR47##wherein X¹ represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁹ is the same or different and is a divalent hydrocarbon radicalcontaining from 4 to 40 carbon atoms, each R¹⁰ is the same or differentand is a substituted or unsubstituted monovalent hydrocarbon radicalcontaining from 1 to 24 carbon atoms, each Ar is the same or differentand represents a substituted or unsubstituted aryl radical, each y isthe same or different and is a value of 0 or 1, Q represents a divalentbridging group selected from --C(R⁵)₂ --, --O--, --S--, --NR⁶⁻, Si(R⁷)₂-- and --CO--, wherein each R⁵ is the same or different and representshydrogen, alkyl radicals having from 1 to 12 carbon atoms, phenyl,tolyl, and anisyl, R⁶ represents hydrogen or a methyl radical, each R⁷is the same or different and represents hydrogen or a methyl radical,and m is a value of 0 or
 1. 13. The process of claim 1 which isconducted at a temperature from about 50° C. to 150° C. and at a totalpressure from about 20 psig to about 3000 psig.
 14. A process forproducing a batchwise or continuously generated reaction mixturecomprising:(1) one or more substituted or unsubstituted6-hydroxyhexanals; (2) optionally one or more substituted orunsubstituted penten-1-ols; (3) optionally one or more substituted orunsubstituted 5-hydroxypentanals and/or cyclic lactol derivativesthereof; (4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof; (5)optionally one or more substituted or unsubstituted pentan-1-ols; (6)optionally one or more substituted or unsubstituted valeraldehydes; (7)optionally one or more substituted or unsubstituted pentenals; (8)optionally one or more substituted or unsubstituted 1,6-hexanedials; (9)optionally one or more substituted 1,5-pentanedials; (10) optionally oneor more substituted 1,4-butanedials; and (11) one or more substituted orunsubstituted butadienes;wherein the weight ratio of component (1) tothe sum of components (2), (3), (4), (5), (6), (7), (8), (9) and (10) isgreater than about 0.1; and the weight ratio of component (11) to thesum of components (1), (2), (3), (4), (5), (6), (7), (8), (9) and (10)is about 0 to about 100; which process comprises reacting one or moresubstituted or unsubstituted butadienes with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst andoptionally free ligand to produce one or more substituted orunsubstituted penten-1-ols, and reacting said one or more substituted orunsubstituted penten-1-ols with carbon monoxide and hydrogen in thepresence of a metal-ligand complex catalyst and optionally free ligandto produce said batchwise or continuously generated reaction mixture.15. A process for producing a batchwise or continuously generatedreaction mixture comprising:(1) one or more substituted or unsubstituted6-hydroxyhexanals; (2) one or more substituted or unsubstitutedpenten-1-ols; (3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof; (4)optionally one or more substituted or unsubstituted 4-hydroxybutanalsand/or cyclic lactol derivatives thereof; and (5) optionally one or moresubstituted or unsubstituted valeraldehydes;wherein the weight ratio ofcomponent (1) to the sum of components (3), (4) and (5) is greater thanabout 0.1; and the weight ratio of component (2) to the sum ofcomponents (1), (3), (4) and (5) is about 0 to about 100; which processcomprises reacting one or more substituted or unsubstituted penten-1-olswith carbon monoxide and hydrogen in the presence of a metal-ligandcomplex catalyst and optionally free ligand to produce said batchwise orcontinuously generated reaction mixture.
 16. A process for producing areaction mixture comprising e or more substituted or unsubstitutedhydroxyaldehydes which process comprises reacting one or moresubstituted or unsubstituted alkadienes with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst andoptionally free ligand to produce one or more substituted orunsubstituted unsaturated alcohols, and reacting said one or moresubstituted or unsubstituted unsaturated alcohols with carbon monoxideand hydrogen in the presence of a metal-ligand complex catalyst andoptionally free ligand to produce said reaction mixture comprising oneor more substituted or unsubstituted hydroxyaldehydes.
 17. A process forproducing a reaction mixture comprising one or more substituted orunsubstituted hydroxyaldehydes which process comprises reacting one ormore substituted or unsubstituted unsaturated alcohols having at least 4carbon atoms with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst and optionally free ligand to produce saidreaction mixture comprising one or more substituted or unsubstitutedhydroxyaldehydes.
 18. A process for producing one or more substituted orunsubstituted 6-hydroxyhexanals which comprises:(a) subjecting one ormore substituted or unsubstituted alkadienes to reductivehydroformylation in the presence of a reductive hydroformylationcatalyst to produce one or more substituted or unsubstituted unsaturatedalcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-ols;(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols from the reductive hydroformylation catalyst; and (c)subjecting said one or more substituted or unsubstituted unsaturatedalcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-olsto hydroformylation in the presence of a hydroformylation catalyst toproduce one or more substituted or unsubstituted 6-hydroxyhexanals. 19.The process of claim 18 wherein the reductive hydroformylationconditions in step (a) and the hydroformylation conditions in step (c)are the same or different, and the reductive hydroformylation catalystin step (a) and the hydroformylation catalyst in step (c) are the sameor different.
 20. A process for producing one or more substituted orunsubstituted 6-hydroxyhexanals which comprises:(a) subjecting one ormore substituted or unsubstituted alkadienes to reductivehydroformylation in the presence of a reductive hydroformylationcatalyst to produce one or more substituted or unsubstituted unsaturatedalcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-ols;(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols from the reductive hydroformylation catalyst; (c)optionally subjecting the 2-penten-1-ols and/or 3-penten-1-ols toisomerization in the presence of a heterogeneous or homogeneous olefinisomerization catalyst to partially or completely isomerize the2-penten-1-ols and/or 3-penten-1-ols to 3-penten-1-ols and/or4-penten-1-ol; and (d) subjecting said one or more substituted orunsubstituted unsaturated alcohols comprising 2-penten-1-ols,3-penten-1-ols and/or 4-penten-1-ol to hydroformylation in the presenceof a hydroformylation catalyst to produce one or more substituted orunsubstituted 6-hydroxyhexanals.
 21. The process of claim 20 wherein thereductive hydroformylation conditions in step (a) and thehydroformylation conditions in step (d) are the same or different, andthe reductive hydroformylation catalyst in step (a) and thehydroformylation catalyst in step (d) are the same or different.
 22. Abatchwise or continuously generated reaction mixture comprising:(1) oneor more substituted or unsubstituted 6-hydroxyhexanals; (2) optionallyone or more substituted or unsubstituted penten-1-ols; (3) optionallyone or more substituted or unsubstituted 5-hydroxypentanals and/orcyclic lactol derivatives thereof; (4) optionally one or moresubstituted or unsubstituted 4-hydroxybutanals and/or cyclic lactolderivatives thereof; (5) optionally one or more substituted orunsubstituted pentan-1-ols; (6) optionally one or more substituted orunsubstituted valeraldehydes; (7) optionally one or more substituted orunsubstituted pentenals; (8) optionally one or more substituted orunsubstituted 1,6-hexanedials; (9) optionally one or more substituted1,5-pentanedials; (10) optionally one or more substituted1,4-butanedials; and (11) one or more substituted or unsubstitutedbutadienes;wherein the weight ratio of component (1) to the sum ofcomponents (2), (3), (4), (5), (6), (7), (8), (9) and (10) is greaterthan about 0.1; and the weight ratio of component (11) to the sum ofcomponents (1), (2), (3), (4), (5), (6), (7), (8), (9) and (10) is about0 to about
 100. 23. A batchwise or continuously generated reactionmixture comprising:(1) one or more substituted or unsubstituted6-hydroxyhexanals; (2) optionally one or more substituted orunsubstituted penten-1-ols; (3) optionally one or more substituted orunsubstituted 5-hydroxypentanals and/or cyclic lactol derivativesthereof; (4) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof; (5)optionally one or more substituted or unsubstituted pentan-1-ols; (6)optionally one or more substituted or unsubstituted valeraldehydes; and(7) one or more substituted or unsubstituted pentenals;wherein theweight ratio of component (1) to the sum of components (2), (3), (4),(5) and (6) is greater than about 0.1; and the weight ratio of component(7) to the sum of components (1), (2), (3), (4), (5) and (6) is about 0to about
 100. 24. A batchwise or continuously generated reaction mixturecomprising:(1) one or more substituted or unsubstituted6-hydroxyhexanals; (2) one or more substituted or unsubstitutedpenten-1-ols; (3) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof; (4)optionally one or more substituted or unsubstituted 4-hydroxybutanalsand/or cyclic lactol derivatives thereof; and (5) optionally one or moresubstituted or unsubstituted valeraldehydes;wherein the weight ratio ofcomponent (1) to the sum of components (3), (4) and (5) is greater thanabout 0.1; and the weight ratio of component (2) to the sum ofcomponents (1), (3), (4) and (6) is about 0 to about
 100. 25. A reactionmixture comprising one or more substituted unsubstitutedhydroxyaldehydes in which said reaction mixture is prepared by a processwhich comprises reacting one or more substituted or unsubstitutedalkadienes with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst and optionally free ligand to produce oneor more substituted or unsubstituted unsaturated alcohols, and reactingsaid one or more substituted or unsubstituted unsaturated alcohols withcarbon monoxide and hydrogen in the presence of a metal-ligand complexcatalyst and optionally free ligand to produce said reaction mixturecomprising one or more substituted or unsubstituted hydroxyaldehydes.26. A reaction mixture comprising one or more substituted orunsubstituted hydroxyaldehydes in which said reaction mixture isprepared by a process which comprises reacting one or more substitutedor unsubstituted unsaturated alcohols having at least 4 carbon atomswith carbon monoxide and hydrogen in the presence of a metal-ligandcomplex catalyst and optionally free ligand to produce said reactionmixture comprising one or more substituted or unsubstitutedhydroxyaldehyde.
 27. The reaction mixture of claim 25 in which theprocess further comprises derivatizing the one or more substituted orunsubstituted hydroxyaldehydess.
 28. The reaction mixture of claim 27 inwhich the derivatizing reaction comprises hydrogenation, esterification,etherification, amination, alkylation, dehydrogenation, reduction,acylation, condensation, carboxylation, carbonylation, oxidation,cyclization, silylation and permissible combinations thereof.